Long-bridged salen catalyst

ABSTRACT

Catalysts comprising long-bridged salen ligands comprising an imino-phenylene-alkylene-imino or an imino-napthalenylene-alkylene-imino bridged salen compound. Also, catalyst systems comprising the catalyst and an activator; methods to prepare the ligands, catalysts and catalyst systems; processes to polymerize olefins using the catalysts and/or catalyst systems; and the olefin polymers prepared according to the processes.

RELATED APPLICATION

This application claims priority to and the benefit of provisionalapplication U.S. 61/837,569 filed Jun. 20, 2013, which is incorporatedby reference herein in its entirety.

FIELD OF THE INVENTION

This invention relates to novel catalyst compounds and catalyst systemscomprising such, methods of preparing such, uses thereof, and productsobtained thereby.

BACKGROUND OF THE INVENTION

Olefin polymerization catalysts are of great use in industry. Hencethere is interest in finding new catalyst systems that increase thecommercial usefulness of the catalyst and allow the production ofpolymers having improved properties.

There is a need in the art for new and improved catalysts and catalystsystems to obtain new and improved polyolefins, polymerizationprocesses, and the like. Accordingly, there is a need in the art for newand improved catalyst systems for the polymerization of olefins for oneor more of the following purposes: to achieve one or more specificpolymer properties, such as high polymer melting point and/or highpolymer molecular weights; to increase conversion or comonomerincorporation; and/or to alter comonomer distribution withoutdeterioration of the properties of the resulting polymer.

SUMMARY OF THE INVENTION

The instant disclosure is directed to catalyst compounds, catalystsystems comprising such compounds, processes for the preparation of thecatalyst compounds and systems, processes for the polymerization ofolefins using such catalyst compounds and systems, and the polyolefinsobtained from such processes. In an embodiment according to theinvention, the catalyst compound comprises Group 3, 4, 5 and/or 6disubstituted compounds supported by a multidentate long-bridged salenligand system coordinated with the metal. In another embodimentaccording to the invention, the catalyst compound comprises Group 3, 4,5 and/or 6 disubstituted compounds supported by a multidentateimino-phenylene-alkylene-imino salen ligand system or animino-naphthalenylene-alkylene-imino salen ligand system, coordinatedwith the metal.

The invention relates to a catalyst compound represented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination;

wherein M is a Group 3, 4, 5 or 6 transition metal;

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen;

wherein n is 1 or 2;

wherein each X is, independently, a univalent C₁ to C₂₀ hydrocarbylradical, a functional group comprising elements from Groups 13-17 of theperiodic table of the elements, or where n is 2 each X may join togetherto form a C₄ to C₆₂ cyclic or polycyclic ring structure;

wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof;

-   -   wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and        R¹² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical,        a functional group comprising elements from Group 13-17 of the        periodic table of the elements, or two or more of R¹ to R¹² may        independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure.

The invention also relates to a catalyst compound represented by theformula:

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen and comprising[O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-fac arrangementor a fac-fac arrangement;

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination;

wherein M is a Group 4, 5 or 6 transition metal;

wherein each of X¹ and X² is, independently, a univalent C₁ to C₂₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or X¹ and X² join togetherto form a C₄ to C₆₂ cyclic or polycyclic ring structure;

wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof;

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.

This invention also relates to catalyst systems comprising suchcompounds, processes for the preparation of the catalyst compounds andsystems, processes for the polymerization of olefins using such catalystcompounds and systems and the polyolefins obtained from such processes.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a representation of molecular structure as determined bysingle crystal X-ray diffraction according to the embodiment of Example4-Ti(O-i-Pr)₂ according to the invention;

FIG. 2 is a representation of molecular structure as determined bysingle crystal X-ray diffraction according to the embodiment of Example10-Zr(O-tert-Bu)₂ according to the invention;

FIG. 3 is a representation of molecular structure as determined bysingle crystal X-ray diffraction according to the embodiment of Example10-Ti(O-i-Pr)₂ according to the invention;

FIG. 4 is a representation of molecular structure as determined bysingle crystal X-ray diffraction according to the embodiment of Example10-Hf(Bn)₂ according to the invention;

FIG. 5 is a representation of molecular structure according to FIG. 4with the phenyl group of each of the benzyl groups omitted for clarity;and

FIG. 6 is a representation of molecular structure as determined bysingle crystal X-ray diffraction according to the embodiment of Example25-Ti(O-i-Pr)₂ according to the invention.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as described inChem. Eng. News, 1985, 63, 27. Therefore, a “Group 4 metal” is anelement from Group 4 of the Periodic Table, e.g., Hf, Ti or Zr.

In the structures depicted throughout this specification and the claims,a solid line indicates a bond; a double line indicates a double bond oran aromatic bond (as between the bridge carbon atoms with substituentsR¹¹ and R¹² in the formulae shown below); and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document unless otherwisespecified. For purposes of this disclosure, a hydrocarbyl radical isdefined to be C₁ to C₇₀ radicals, or C₁ to C₂₀ radicals, or C₁ to C₁₀radicals, or C₆ to C₇₀ radicals, or C₆ to C₂₀ radicals, or C₇ to C₂₀radicals that may be linear, branched, or cyclic where appropriate(aromatic or non-aromatic); and includes hydrocarbyl radicalssubstituted with other hydrocarbyl radicals and/or one or morefunctional groups comprising elements from Groups 13-17 of the periodictable of the elements. In addition two or more such hydrocarbyl radicalsmay together form a fused ring system, including partially or fullyhydrogenated fused ring systems, which may include heterocyclicradicals.

The term “substituted” means that a hydrogen atom and/or a carbon atomin the base structure has been replaced with a hydrocarbyl radical,and/or a functional group, and/or a heteroatom or a heteroatomcontaining group. Accordingly, the term hydrocarbyl radical includesheteroatom containing groups. For purposes herein, a heteroatom isdefined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group, which is the base structure,substituted with a methyl radical, which may also be referred to as amethyl functional group, ethyl alcohol is an ethyl group, which is thebase structure, substituted with an —OH functional group, and pyridineis a phenyl group having a carbon in the base structure of the benzenering substituted with a nitrogen atom.

For purposes herein, a hydrocarbyl radical may be independently selectedfrom substituted or unsubstituted methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, andtriacontynyl.

For purposes herein, hydrocarbyl radicals may also include isomers ofsaturated, partially unsaturated and aromatic cyclic structures whereinthe radical may additionally be subjected to the types of substitutionsdescribed above. The term “aryl”, “aryl radical”, and/or “aryl group”refers to aromatic cyclic structures, which may be substituted withhydrocarbyl radicals and/or functional groups as defined herein.Examples of aryl radicals include: acenaphthenyl, acenaphthylenyl,acridinyl, anthracenyl, benzanthracenyl, benzimidazolyl, benzisoxazolyl,benzofluoranthenyl, benzofuranyl, benzoperylenyl, benzopyrenyl,benzothiazolyl, benzothiophenyl, benzoxazolyl, benzyl, carbazolyl,carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl, cyclohexenyl,methylcyclohexyl, dibenzoanthracenyl, fluoranthenyl, fluorenyl, furanyl,imidazolyl, indazolyl, indenopyrenyls, indolyl, indolinyl,isobenzofuranyl, isoindolyl, isoquinolinyl, isoxazolyl, methyl benzyl,methylphenyl, naphthyl, oxazolyl, phenanthrenyl, phenyl, purinyl,pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl, pyrimidinyl,pyrrolyl, quinazolinyl, quinolonyl, quinoxalinyl, thiazolyl, thiophenyl,and the like.

It is to be understood that for purposes herein, when a radical islisted, it indicates that the base structure of the radical (the radicaltype) and all other radicals formed when that radical is subjected tothe substitutions defined above. Alkyl, alkenyl, and alkynyl radicalslisted include all isomers including where appropriate cyclic isomers,for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (and cyclobutenylsand cyclopropenyls). Cyclic compounds having substitutions include allisomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

Likewise the terms “functional group”, “group” and “substituent” arealso used interchangeably throughout this document unless otherwisespecified. For purposes herein, a functional group includes both organicand inorganic radicals and moieties comprising elements from Groups 13,14, 15, 16, and 17 of the periodic table of elements. Suitablefunctional groups may include hydrocarbyl radicals, e.g., alkylradicals, alkene radicals, aryl radicals, and/or halogen (Cl, Br, I, F),also referred to herein as “halo”, O, S, Se, Te, NR*_(x), OR*, SeR*,TeR*, PR*_(x), AsR*_(x), SbR*_(x), SR*, BR*_(x), SiR*_(x), GeR*_(x),SnR*_(x), PbR*_(x), and/or the like, wherein R* is a C₁ to C₂₀hydrocarbyl as defined above and wherein x is the appropriate integer toprovide an electron neutral moiety. Other examples of functional groupsinclude those typically referred to as amines, imides, amides, ethers,alcohols (hydroxides), sulfides, sulfates, phosphides, halides,phosphonates, alkoxides, esters, carboxylates, aldehydes, and the like.

For purposes herein “direct bonds,” “direct covalent bonds” or “directlybridged” are used interchangeably to refer to covalent bonds directlybetween atoms that do not have any intervening atoms.

For purposes herein an “olefin,” alternatively referred to as “alkene,”is a linear, branched, or cyclic compound comprising carbon and hydrogenhaving at least one double bond. For purposes of this specification andthe claims appended thereto, when a polymer or copolymer is referred toas comprising an olefin, the olefin present in such polymer or copolymeris the polymerized form of the olefin. For example, when a copolymer issaid to have an “ethylene” content of 35 wt % to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from ethylenein the polymerization reaction and said derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer.

For purposes herein a “polymer” has two or more of the same or different“mer” units. A “homopolymer” is a polymer having mer units that are thesame. A “copolymer” is a polymer having two or more mer units that aredifferent from each other. A “terpolymer” is a polymer having three merunits that are different from each other. “Different” in reference tomer units indicates that the mer units differ from each other by atleast one atom or are different isomerically. Accordingly, thedefinition of copolymer, as used herein, includes terpolymers and thelike. An oligomer is typically a polymer having a low molecular weight,such as an Mn of less than 25,000 g/mol, or in an embodiment accordingto the invention less than 2,500 g/mol, or a low number of mer units,such as 75 mer units or less. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mole %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mole % propylenederived units, and so on.

For the purposes of this disclosure, the term “α-olefin” includes C₂-C₂₂olefins. Non-limiting examples of α-olefins include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene,1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The terms “catalyst”, “catalyst compound”, and “transition metalcompound” are defined to mean a compound capable of initiatingpolymerization catalysis under the appropriate conditions. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor. A “catalyst system”is combination of at least one catalyst compound, at least oneactivator, an optional co-activator, and an optional support material,where the system can polymerize monomers to polymer. For the purposes ofthis invention and the claims thereto, when catalyst systems aredescribed as comprising neutral stable forms of the components it iswell understood by one of ordinary skill in the art that the ionic formof the component is the form that reacts with the monomers to producepolymers.

For purposes herein the term “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W g of catalyst (cat), over a period of time of T hours; andmay be expressed by the following formula: P(T×W) and expressed in unitsof gPgcat⁻¹ hr⁻¹. Conversion is the amount of monomer that is convertedto polymer product, and is reported as mol % and is calculated based onthe polymer yield and the amount of monomer fed into the reactor.Catalyst activity is a measure of how active the catalyst is and isreported as the mass of product polymer (P) produced per mole ofcatalyst (cat) used (kg P/mol cat).

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A scavenger is a compound that is typically added to facilitatepolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In an embodiment according to theinvention a co-activator can be pre-mixed with the catalyst compound toform an alkylated catalyst compound.

As used herein, Mn is number average molecular weight as determined byproton nuclear magnetic resonance spectroscopy (¹H NMR) unless statedotherwise, Mw is weight average molecular weight determined by gelpermeation chromatography (GPC), and Mz is z average molecular weightdetermined by GPC, wt % is weight percent, and mol % is mole percent.Molecular weight distribution (MWD) is defined to be Mw divided by Mn.Unless otherwise noted, all molecular weight units, e.g., Mw, Mn, Mz,are reported in g/mol.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iso-butyl is isobutyl, sec-butylrefers to secondary butyl, tert-butyl, t-butyl, tert-Bu, or t-Bu refersto tertiary butyl, n-butyl is normal butyl, pMe is para-methyl, Bn isbenzyl, THF is tetrahydrofuran, Mes is mesityl, also known as1,3,5-trimethylbenzene, Tol is toluene, TMS is trimethylsilyl, TIBAL istriisobutylaluminum, TNOAL is triisobutyl n-octylaluminum, MAO ismethylalumoxane, MOMO is methoxymethoxy (also referred to asmethoxymethyl ether), N is nitrogen (including that N^(a), N^(b), N¹, N²are nitrogen) and O is oxygen (including that O^(a), O^(b), O¹, O² areoxygen). Further, N^(a) and N¹, N² and N^(b), O^(a) and O¹, and O^(b)and O² are equivalent and may be used interchangeably between formulae.

For purposes herein whenever a composition, an element or a group ofelements is preceded with the transitional phrase “comprising”, it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of”, “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

For purposes herein, RT is room temperature, which is defined as 25° C.unless otherwise specified. All percentages are weight percent (wt %)unless otherwise specified.

In the description herein, the salen catalyst may be described as acatalyst precursor, a pre-catalyst compound, a salen catalyst compoundor a transition metal compound, and these terms are usedinterchangeably.

Polypropylene microstructure is determined by ¹³C-NMR spectroscopy,including the concentration of isotactic and syndiotactic dyads ([m] and[r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Thedesignation “m” or “r” describes the stereochemistry of pairs ofcontiguous propylene groups, “m” referring to meso and “r” to racemic.Samples are dissolved in d₂-1,1,2,2-tetrachloroethane, and spectrarecorded at 125° C. using a 100 MHz (or higher) NMR spectrometer.Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculationsinvolved in the characterization of polymers by NMR are described by F.A. Bovey in Polymer Conformation and Configuration (Academic Press, NewYork 1969) and J. Randall in Polymer Sequence Determination, ¹³C-NMRMethod (Academic Press, New York, 1977).

Melting point (Tm or Tmelt), also referred to as melting temperature,and heat of fusion (Hf) of polymers are determined using differentialscanning calorimetry (DSC) on a commercially available instrument (e.g.,TA Instruments 2920 DSC). Typically, 6 to 10 mg of molded polymer orplasticized polymer are sealed in an aluminum pan and loaded into theinstrument at room temperature. Melting data (first heat) is acquired byheating the sample to at least 30° C. above its melting temperature,typically 220° C. for polypropylene, at a heating rate of 10° C./min.The sample is held for at least 5 minutes at this temperature to destroyits thermal history. Crystallization data are acquired by cooling thesample from the melt to at least 50° C. below the crystallizationtemperature, typically −50° C. for polypropylene, at a cooling rate of20° C./min. The sample is held at this temperature for at least 5minutes, and finally heated at 10° C./min to acquire additional meltingdata (second heat). The endothermic melting transition (first and secondheat) and exothermic crystallization transition are analyzed accordingto standard procedures. The melting temperatures reported are the peakmelting temperatures from the second heat unless otherwise specified.

For polymers displaying multiple peaks, the melting temperature isdefined to be the peak melting temperature from the melting traceassociated with the largest endothermic calorimetric response (asopposed to the peak occurring at the highest temperature). Areas underthe DSC curve are used to determine the heat of transition (heat offusion, H_(f), upon melting), which can be used to calculate the degreeof crystallinity (also called the percent crystallinity). The percentcrystallinity (X %) is calculated using the formula: [area under thecurve (in J/g)/H° (in J/g)]*100, where H° is the ideal heat of fusionfor a perfect crystal of the homopolymer of the major monomer component.These values for H° are to be obtained from the Polymer Handbook, FourthEdition, published by John Wiley and Sons, New York 1999, except that avalue of 290 J/g is used for H° (polyethylene), a value of 140 J/g isused for H° (polybutene), and a value of 207 J/g is used for H°(polypropylene).

For purposes herein, a chiral carbon is indicated by a C* and/or atleast two of the substituents are indicated using the flying wedge anddotted wedge depictions known in the art. For purposes herein, unlessotherwise specified, a structure comprising a chiral carbon, whetherexpressly indicated or not, includes the enantiomerically pure compoundor compounds in the case of multiple chiral carbons, the racemic mixtureof compounds, or a combination thereof, including racemic mixturescombined with enantiomerically pure isomers in the case of multiplechiral carbons present in the same molecule.

For purposes herein, a bulky ligand substitution on animino-phenylene-alkylene-imino salen catalyst compound (e.g.,imino-benzylimine salen catalyst compound when the alkylene group ismethylene) is defined as a C₄ to C₂₀ hydrocarbyl radical; —SR^(a),—NR^(a) ₂ and —PR^(a) ₂, where each R^(a) is independently a C₄ to C₂₀hydrocarbyl; or a C₄ to C₂₀ hydrocarbyl substituted organometalloid. Themolecular volume of a substituent is used herein as an approximation ofspatial steric bulk. Comparison of substituents with differing molecularvolumes allows the substituent with the smaller molecular volume to beconsidered “less bulky” in comparison to the substituent with the largermolecular volume. Conversely, a substituent with a larger molecularvolume may be considered “more bulky” than a substituent with a smallermolecular volume.

Molecular volume may be calculated as reported in “A Simple ‘Back of theEnvelope’Method for Estimating the Densities and Molecular Volumes ofLiquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11,November 1994, pp. 962-964. Molecular volume (MV), in units of cubic Å,is calculated using the formula: MV=8.3 Vs, where Vs is the scaledvolume. Vs is the sum of the relative volumes of the constituent atoms,and is calculated from the molecular formula of the substituent usingthe following table of relative volumes. For fused rings, the Vs isdecreased by 7.5% per fused ring.

Element Relative Volume, Å (Vs) H 1 1^(st) short period, Li to F 22^(nd) short period, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd)long period, Rb to I 7.5 3^(rd) long period, Cs to Bi 9

For purposes herein, a bulky substituent is defined as any substituenthaving a molecular volume greater than or equal to a tertiary-butylsubstitution (MV=8.3 Vs=141.1). Examples of other suitable bulkysubstituents include adamantyl, halo substituted and unsubstituted arylfunctional groups, and the like.

For purposes herein, a long-bridged salen catalyst compound refers to atetradentate ligand system comprising a first arm connected to a secondarm by a bridge an imino-alkenylene-alkylene-imino, wherein the bridgecomprises a backbone of at least 3 carbon atoms, e.g., animino-phenylene-alkylene-imino bridge is an imino-benzylimine salen whenthe alkylene is methylene. In embodiments according to the invention thefirst arm comprises an imine-phenolate moiety bound to an olefinic oraromatic carbon (sp²) of the bridge, e.g., the imino portion of theimino-phenylene-alkylene-imino bridge embodiment, and the second armcomprises an imine-phenolate moiety bound to an aliphatic (sp³) carbonatom, e.g., the alkylene-imine portion of theimino-phenylene-alkylene-imino bridge embodiment. Accordingly, thebridge between the two imino-phenolate ligand arms is asymmetric.

As shown below, the long-bridged or imino-phenylene-alkylene-iminobridged salen ligand system includes [O^(a),N^(a),N^(b),O^(b)] whereO^(a) and N^(a) are attached to a first arm of the ligand, N^(b)) andO^(b) are attached to a second arm of the ligand, and the first andsecond ligands are attached to each other by a bridge moiety Y betweenN^(a) and N^(b) (O=oxygen and N=nitrogen). Each of O^(a), N^(a), N^(b),and O^(b) are coordinated with the metal atom. For purposes herein along-bridged salen catalyst compound has one of the general structures Ior II:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination and where R¹ to R¹², M, n, X¹, X² and Y are asdescribed below.

For purposes herein, a “fac” (facial) configuration refers to a salenligand structure (II) where O^(a) and/or O^(b) is not in the[N^(a),N^(b),M] plane in a six-coordinated arrangement centered aroundthe metal atom, or stated differently, all three of the atoms[O^(a),N^(a),N^(b)] and/or all three of the atoms [N^(a),N^(b),O^(b)]are on the same side ([O^(a), N^(b)] and [N^(a),O^(b)] are located cis);whereas in a “mer” (meridional) configuration, O^(a) and/or O^(b) are inthe [N^(a),N^(b),M] plane, or stated differently, O^(a) is on theopposite side of the metal center (located trans) with respect to N^(b)and/or O^(b) is on the opposite side of the metal center or trans withrespect to N^(a). For purposes herein, in the binary wrapping modedesignations, the configuration of [O^(a),N^(a),N^(b)] is stated firstand [N^(a),N^(b),O^(b)] second, e.g., “fac-mer” refers to fac[O^(a),N^(a),N^(b)] and mer [N^(a),N^(b),O^(b)].

The four arrangements of the O^(a)—N^(a)—N^(b)—O^(b) salen catalystcompounds which are possible are: mer-mer, also referred to in the artas trans with respect to the labile groups X¹ and X²; fac-fac, alsoreferred to in the art as cis-alpha; and fac-mer and mer-fac, both ofwhich are generally referred to as cis-beta, but which are actuallydifferent isomers as illustrated below.

Catalyst Compounds

In an embodiment according to the invention, the catalyst comprisesGroup 3, 4, 5 and/or 6 dialkyl compounds supported by a tetradentatedi-anionic long-bridged salen ligand, and in embodiments according tothe invention may be useful to polymerize olefins and/or α-olefins toproduce polyolefins and/or poly(α-olefins).

In an embodiment according to the invention, the catalyst compounds arerepresented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; wherein M is a Group 3, 4, 5 or 6 transitionmetal; wherein N¹ and N² are nitrogen and O¹ and O² are oxygen; whereinn is 1 or 2; wherein each X is, independently, a univalent C₁ to C₂₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or where n is 2 each X mayjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure;wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof; wherein eachof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.

In a particular embodiment according to the invention, the catalystcompounds are represented by the formula:

comprising [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-facarrangement; wherein each solid line represents a covalent bond and eachdashed line represents a bond having varying degrees of covalency and avarying degree of coordination; wherein M is a Group 4, 5 or 6transition metal; wherein N¹ and N² are nitrogen and O¹ and O² areoxygen; wherein each of X¹ and X² is, independently, a univalent C₁ toC₂₀ hydrocarbyl radical, a functional group comprising elements fromGroups 13-17 of the periodic table of the elements, or X¹ and X² jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure;wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof; wherein eachof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.

According to a particular embodiment according to the invention, M isTi, Hf or Zr. In one embodiment, M is Ti. In an embodiment according tothe invention, X¹ and X² is each a benzyl radical or a halogen radical.

In an embodiment according to the invention, each R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is, independently, hydrogen, ahalogen, or a C₁ to C₃₀ hydrocarbyl radical.

In an embodiment according to the invention, each R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is, independently, hydrogen, ahalogen, or a C₁ to C₁₀ hydrocarbyl radical.

According to a particular embodiment, the sp3 carbon directly bonded toN² is a benzylic carbon. In an embodiment according to the invention, Yis a divalent aliphatic radical having from 1 to 10 carbon atoms.

According to a particular embodiment of the invention, the catalystcompound is an imino-phenylene-alkylene-imino bridged salen ligandsystem coordinated with the metal, wherein R¹¹ and R¹² join to form aphenylene ring directly bonded to N¹ and the alkylene group or moiety Yis bonded to the phenylene ring and to N², as represented by theformulae:

wherein M, n, X, X¹, and X² are as described above; and wherein each ofR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, and R¹⁶ isindependently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹⁰ and R¹³ to R¹⁶ may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure.

According to a particular embodiment according to the invention, thecatalyst is represented by the formulae:

wherein M, n. X, X¹, and X² are as described above; and wherein each ofR¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, andR¹⁸ is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R¹⁰ and R¹³ to R¹⁸ mayindependently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure.

According to a particular embodiment according to the invention, R¹⁴ andR¹⁵ of the phenylene moiety join to form a 2,3-naphthalenylene ringdirectly bonded to N² and Y to form animino-naphthalenylene-alkylene-imino bridged salen compound, representedby the formula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁶, R¹⁹,R²⁰, R²¹, and R²² is independently, a hydrogen, a C₁-C₄₀ hydrocarbylradical, a functional group comprising elements from Group 13-17 of theperiodic table of the elements, or two or more of R¹ to R¹⁰ and R¹³ toR¹⁶ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.

In a particular embodiment according to the invention: X¹ and X² arebenzyl radicals; at least one of R¹, R², R⁴, R⁵, R⁷, and R⁸ areindependently selected from the group consisting of: C₁-C₁₀ alkyl,C₁-C₁₀ cycloalkyl, C₁-C₁₀ alkenyl C₁-C₁₀ alkoxy, aryl substituted C₁-C₁₀alkyl, C₁-C₁₀ aryl, halo, and combinations thereof; and R³, R⁶, R⁹, R¹⁰,R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are hydrogen.

In a particular embodiment according to the invention, at least one ofR¹, R², R⁴, R⁵, R⁷, and R⁸ are independently selected from the groupconsisting of: methyl, ethyl, isopropyl, isobutyl, tertiary-butyl,isopentyl, 2-methyl-2-phenylethyl; methoxy, benzyl, adamantyl, chloro,bromo, iodo, and combinations thereof.

In a particular embodiment according to the invention, R² and R⁴ areidentical, R⁵ and R⁷ are identical, or a combination thereof.

In an embodiment according to the invention, a catalyst systemcomprises: an activator and a catalyst compound represented by theformula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; wherein M is a Group 3, 4, 5 or 6 transitionmetal; wherein N¹ and N² are nitrogen and O¹ and O² are oxygen; whereinn is 1 or 2; wherein each X is, independently, a univalent C₁ to C₂₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or where n is 2 each X mayjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure;wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof; wherein eachof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.

In an embodiment according to the invention, a catalyst systemcomprises: an activator and a catalyst compound represented by theformula:

comprising [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-facarrangement, or wherein activation of the catalyst compound rearranges[O¹,N¹,N²]—[N¹N²,O²] into a fac-mer arrangement or a mer-facarrangement; wherein each solid line represents a covalent bond and eachdashed line represents a bond having varying degrees of covalency and avarying degree of coordination; wherein M is a Group 3, 4, 5 or 6transition metal; wherein N¹ and N² are nitrogen and O¹ and O² areoxygen; wherein each of X¹ and X² is, independently, a univalent C₁ toC₂₀ hydrocarbyl radical, a functional group comprising elements fromGroups 13-17 of the periodic table of the elements, or X¹ and X² jointogether to form a C₄ to C₆₂ cyclic or polycyclic ring structure;wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof; wherein eachof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.

In a particular embodiment according to the invention, the catalystsystem comprises [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement; orwherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-merarrangement.

In an embodiment according to the invention, the activator comprisesalumoxane, a non-coordinating anion activator or a combination thereof.In a particular embodiment, the activator comprises alumoxane and thealumoxane is present at a ratio of 1 mole aluminum or more per mole ofcatalyst compound.

In a particular embodiment according to the invention, the activator isrepresented by the formula: (Z)_(d) ⁺(A^(d−)) wherein Z is (L-H), or areducible Lewis Acid, wherein L is a neutral Lewis base, H is hydrogenand (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinating anion havingthe charge d⁻; and d is an integer from 1 to 3.

In an embodiment according to the invention, the activator isrepresented by the formula: (Z)_(d) ⁺(A^(d−)) wherein A^(d−) is anon-coordinating anion having the charge d⁻; d is an integer from 1 to3, and Z is a reducible Lewis acid represented by the formula: (Ar₃C⁺),where Ar is aryl radical, an aryl radical substituted with a heteroatom,an aryl radical substituted with one or more C₁ to C₄₀ hydrocarbylradicals, an aryl radical substituted with one or more functional groupscomprising elements from Groups 13-17 of the periodic table of theelements, or a combination thereof.

In an embodiment according to the invention, a process to activate acatalyst system comprises combining an activator with a catalystcompound represented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; wherein M is a Group 3, 4, 5 or 6 transitionmetal; wherein N¹ and N² are nitrogen and O¹ and O² are oxygen; whereinn is 1 or 2; wherein each X is, independently, a univalent C₁ to C₂₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or where n is 2 each X mayjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure;wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof; wherein eachof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.

In an embodiment according to the invention, a process to activate acatalyst system comprises combining an activator with a catalystcompound represented by the formula:

comprising [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-facarrangement or a fac-fac arrangement, or wherein activation rearranges[O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement or a mer-facarrangement or a fac-fac arrangement; wherein each solid line representsa covalent bond and each dashed line represents a bond having varyingdegrees of covalency and a varying degree of coordination; wherein M isa Group 3, 4, 5 or 6 transition metal; wherein N¹ and N² are nitrogenand O¹ and O² are oxygen; wherein each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; wherein Y comprises an sp³ carbon directly bonded to N² andis selected from the group consisting of divalent C₁ to C₄₀ hydrocarbylradicals, divalent functional groups comprising elements from Groups13-17 of the periodic table of the elements, and combinations thereof;and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, andR¹² is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R¹² may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure.Methods to Prepare the Catalyst Compounds.

In an embodiment according to the invention, the transition metalcompounds may be prepared by an imine-condensation procedure if analdehyde located ortho to a hydroxy functional group (e.g., asubstituted salicylaldehyde base structure) is used (reaction A). In anembodiment according to the invention where both sides of the salenligand are identically substituted (R′ is identical to R), twoequivalents of the salicylaldehyde may be used. In an embodimentaccording to the invention where the two sides of the salen ligand arenot identically substituted (R′ is not identical to R), two sequentialcondensation steps may be used. The long-bridged (e.g.,imino-phenylene-alkylene-imino bridged) salen ligand, which is iminobenzylimine bridged when the alkylene Y moiety is methylene) is thenconverted into the metal substituted catalyst precursor by reaction witha metalation reagent MX_((n+2)) where n is 1 or 2, e.g., a metal tri- ortetra-substituted compound to yield the finished complex (reaction B1)or into the metal di-substituted catalyst precursor by reaction with ametalation reagent MX₄, e.g., a metal tetra-substituted compound toyield the finished complex (reaction B2).

Reaction A:

Reaction B1:

Reaction B2:

In embodiments according to the invention, the salen ligand may becontacted with the metalation reagent in Reaction B1 or in Reaction B2to form the catalyst compound prior to combination with the activator,and subsequently the catalyst compound may be contacted with theactivator, with or without isolation of the precursor catalyst compound,or the salen ligand and the metalation reagent may be contacted inReaction B1 or in Reaction B2 in the presence of the activator, in thepresence of one or more olefins, or a combination thereof, e.g., in anin situ metalation, activation and/or polymerization process.

In an embodiment according to the invention, the transition metalcompounds may comprise salen ligands in which theimino-phenylene-alkylene-imino bridge is modified to comprise anaphthalenylene or larger polycyclic aromatic hydrocarbon moiety (e.g.,wherein the imino-phenylene-alkylene-imino bridge moiety comprises atleast one additional conjugated phenyl ring, such as, for example,anthracene, a benzopyrene, a benzoperylene, chrysene, phenanthrene,tetracene, triphenylene, and the like). In an embodiment according tothe invention, the transition metal compound comprises animino-phenylene-alkylene-imino bridged salen compound represented by theformula:

wherein the alkylene moiety Y comprises an sp³ carbon directly bonded toN² and is selected from the group consisting of divalent C₁ to C₄₀hydrocarbyl radicals, divalent functional groups comprising elementsfrom Groups 13-17 of the periodic table of the elements, andcombinations thereof;wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁶, R¹⁹,R²⁰, R²¹, and R²² is independently, a hydrogen, a C₁-C₄₀ hydrocarbylradical, a functional group comprising elements from Group 13-17 of theperiodic table of the elements, or two or more of R¹ to R¹⁰ and R¹³ toR¹⁶ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.

In an embodiment according to the invention, the phenylene-based bridgeis modified to include a naphthalenylene moiety to form a moreconjugated bridge which is more electron-withdrawing and has a morecrystalline character than the phenylene-based bridge. In an embodimentaccording to the invention, modifications of the di-imino bridge may beused to obtain an advantage in tuning for a specific catalyst activityand/or desired polymer properties.

In an embodiment according to the invention,2-aminomethyl-3-aminonaphthalene, which is a commercially availablecompound, may undergo condensation with 2 equivalents of substitutedsalicylaldehydes as described herein to form the correspondinglong-salen ligand precursor in a single step. In embodiments,modification of the synthetic scheme may also lead to ligands with twodifferent phenol arms. Reacting these ligand precursors with group 4metal precursors such as MBn₄ (M=Ti, Zr, Hf) as described herein lead tothe desired precatalysts in a single step. These precatalysts can beactivated by common cocatalysts such as MAO and the like, leading toactive catalysts for stereoregular polymerization of alpha-olefinsincluding propylene.

Examples of imino-naphthalenylene-alkylene-imino bridged salenprecursors and complexes include:

In an embodiment according to the invention, the long-bridge salenligand may further comprise ortho-carbazole substituents on the phenolrings; the carbazole substituents being both aromatic and electronwithdrawing. In an embodiment according to the invention thelong-bridged salen ligand precursor may include carbazole substituentson the two phenol arms, as shown in Reaction C. Modification of thesynthetic scheme may lead to long-bridged salen ligand precursor inwhich one of the phenol arms bears the carbazole substituent and theother phenol arm bears a different substitution pattern. Reacting theseligand precursors with group 4 metal precursors such as MBn₄ (M=Ti, Zr,Hf) as described herein lead to the desired precatalysts in a singlestep.

Reaction C:

In an embodiment of the invention, the long-bridged salen compoundcomprises a 2,3 substituted naphthalenylene ring directly bonded to N²and a C₁-C₄₀ alkylene moiety Y to form animino-naphthalenylene-alkylene-imino bridged salen compound representedby the formula:

comprising [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-facarrangement or a fac-fac arrangement;

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination;

wherein M is a Group 4, 5 or 6 transition metal;

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen;

wherein each of X¹ and X² is, independently, a univalent C₁ to C₂₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or X¹ and X² join togetherto form a C₄ to C₆₂ cyclic or polycyclic ring structure;

wherein Y comprises an sp³ carbon directly bonded to N² and is selectedfrom the group consisting of divalent C₁ to C₄₀ hydrocarbyl radicals,divalent functional groups comprising elements from Groups 13-17 of theperiodic table of the elements, and combinations thereof;

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁶, R¹⁹,R²⁰, R²¹, and R²² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbylradical, a functional group comprising elements from Group 13-17 of theperiodic table of the elements, or two or more of R¹ to R¹⁰ and R¹³ toR¹⁶ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.

Activators

The terms “cocatalyst” and “activator” are used interchangeably todescribe activators and are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts. Activators may includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment according to the invention, alumoxane activators areutilized as an activator in the catalyst composition. Alumoxanes aregenerally oligomeric compounds containing —Al(R¹)—O— sub-units, where R¹is an alkyl radical. Examples of alumoxanes include methylalumoxane(MAO), modified methylalumoxane (MMAO), ethylalumoxane andisobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes aresuitable as catalyst activators, particularly when the catalystprecursor compound comprises an abstractable ligand which is an alkyl,halide, alkoxide or amide. Mixtures of different alumoxanes and modifiedalumoxanes may also be used. In an embodiment according to theinvention, visually clear methylalumoxane may be used. A cloudy orgelled alumoxane can be filtered to produce a clear solution or clearalumoxane can be decanted from the cloudy solution. A useful alumoxaneis a modified methyl alumoxane (MMAO) described in U.S. Pat. No.5,041,584 and/or commercially available from Akzo Chemicals, Inc. underthe trade designation Modified Methylalumoxane type 3A.

When the activator is an alumoxane (modified or unmodified), in anembodiment according to the invention, the maximum amount of activatoris typically at a 5000-fold molar excess Al/M over the catalyst compound(per metal catalytic site). In an embodiment according to the invention,the minimum activator-to-catalyst-compound, which is determinedaccording to molar concentration of the transition metal M, in anembodiment according to the invention is 1 mole aluminum or less to moleof transition metal M. In an embodiment according to the invention, theactivator comprises alumoxane and the alumoxane is present at a ratio of1 mole aluminum or more to mole of catalyst compound. In an embodimentaccording to the invention, the minimum activator-to-catalyst-compoundmolar ratio is a 1:1 molar ratio. Other embodiments according to theinvention of Al:M ranges include from 1:1 to 500:1, or from 1:1 to200:1, or from 1:1 to 100:1, or from 1:1 to 50:1.

In an embodiment according to the invention, little or no alumoxane(i.e., less than 0.001 wt %) is used in the polymerization processesdescribed herein. In an embodiment according to the invention, alumoxaneis present at 0.00 mole %, or the alumoxane is present at a molar ratioof aluminum to catalyst compound transition metal less than 500:1, orless than 300:1, or less than 100:1, or less than 1:1.

The term “non-coordinating anion” (NCA) refers to an anion which eitherdoes not coordinate to a cation, or which is only weakly coordinated toa cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral transitionmetal compound and a neutral by-product from the anion. Non-coordinatinganions useful in accordance with this invention are those that arecompatible with the polymerization or catalyst system, stabilize thetransition metal cation in the sense of balancing its ionic charge at+1, and yet are sufficiently labile to permit displacement duringpolymerization.

In an embodiment according to the invention, an ionizing orstoichiometric activator may be used, which may be neutral or ionic,such as tri(n-butyl) ammonium boron metalloid precursor, polyhalogenatedheteroborane anions (WO 98/43983), boric acid (U.S. Pat. No. 5,942,459),or a combination thereof. In an embodiment according to the invention,neutral or ionic activators alone or in combination with alumoxane ormodified alumoxane activators may be used.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium, and indium, or mixtures thereof.The three substituent groups or radicals can be the same or differentand in an embodiment according to the invention are each independentlyselected from substituted or unsubstituted alkyls, alkenyls, alkyns,aryls, alkoxy, and halogens. In an embodiment according to theinvention, the three groups are independently selected from halogen,mono or multicyclic (including halosubstituted) aryls, alkyls, andalkenyl compounds, and mixtures thereof; or independently selected fromalkenyl radicals having 1 to 20 carbon atoms, alkyl radicals having 1 to20 carbon atoms, alkoxy radicals having 1 to 20 carbon atoms and aryl orsubstituted aryl radicals having 3 to 20 carbon atoms. In an embodimentaccording to the invention, the three substituent groups are alkylradicals having 1 to 20 carbon atoms, phenyl, naphthyl, or mixturesthereof. In an embodiment according to the invention, the three groupsare halogenated aryl groups, e.g., fluorinated aryl groups. In anembodiment according to the invention the neutral stoichiometricactivator is tris perfluorophenyl boron or tris perfluoronaphthyl boron.

In an embodiment according to the invention, ionic stoichiometricactivator compounds may include an active proton, or some other cationassociated with, but not coordinated to, or only loosely coordinated tothe remaining ion of the ionizing compound. Suitable examples includecompounds and the like described in European publications EP 0 570 982A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0277 004 A; U.S. Pat. Nos. 5,153,157; 5,198,401; 5,066,741; 5,206,197;5,241,025; 5,384,299; 5,502,124; and WO 1996/04319; all of which areherein fully incorporated by reference.

In an embodiment according to the invention compounds useful as anactivator comprise a cation, which is, for example, a Bronsted acidcapable of donating a proton, and a compatible non-coordinating anionwhich anion is relatively large (bulky), capable of stabilizing theactive catalyst species (the Group 4 cation, e.g.) which is formed whenthe two compounds are combined and said anion will be sufficientlylabile to be displaced by olefinic, diolefinic or acetylenicallyunsaturated substrates or other neutral Lewis bases, such as ethers,amines, and the like. Two classes of useful compatible non-coordinatinganions are disclosed in EP 0 277 003 A1, and EP 0 277 004 A1, whichinclude anionic coordination complexes comprising a plurality oflipophilic radicals covalently coordinated to and shielding a centralcharge-bearing metal or metalloid core; and anions comprising aplurality of boron atoms such as carboranes, metallacarboranes, andboranes.

In an embodiment according to the invention, the stoichiometricactivators include a cation and an anion component, and may berepresented by the following formula (1):(Z)_(d) ⁺(A^(d−))  (1)wherein Z is (L-H) or a reducible Lewis Acid, L is a neutral Lewis base;H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinatinganion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)_(d) ⁺, thecation component may include Bronsted acids such as protonated Lewisbases capable of protonating a moiety, such as an alkyl or aryl, fromthe catalyst precursor, resulting in a cationic transition metalspecies, or the activating cation (L-H)_(d) ⁺ is a Bronsted acid,capable of donating a proton to the catalyst precursor resulting in atransition metal cation, including ammoniums, oxoniums, phosphoniums,silyliums, and mixtures thereof, or ammoniums of methylamine, aniline,dimethylamine, diethylamine, N-methylaniline, diphenylamine,trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine,pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline,phosphoniums from triethylphosphine, triphenylphosphine, anddiphenylphosphine, oxoniums from ethers, such as dimethyl ether diethylether, tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid it may be represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In an embodiment accordingto the invention, the reducible Lewis acid is triphenyl carbenium.

Embodiments according to the invention of the anion component A^(d−)include those having the formula [M^(k+)Q_(n)]^(d−) wherein k is 1, 2,or 3; n is 1, 2, 3, 4, 5 or 6, or 3, 4, 5 or 6; n−k=d; M is an elementselected from Group 13 of the Periodic Table of the Elements, or boronor aluminum, and Q is independently a hydride, bridged or unbridgeddialkylamido, halide, alkoxide, aryloxide, hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide, and two Q groups may form a ring structure.Each Q may be a fluorinated hydrocarbyl radical having 1 to 20 carbonatoms, or each Q is a fluorinated aryl radical, or each Q is apentafluoryl aryl radical. Examples of suitable A^(d−) components alsoinclude diboron compounds as disclosed in U.S. Pat. No. 5,447,895, whichis fully incorporated herein by reference.

In an embodiment according to the invention, this invention relates to amethod to polymerize olefins comprising contacting olefins (e.g.,ethylene and/or propylene) with a long-bridged (e.g.,imino-phenylene-alkylene-imino bridged) salen catalyst compound, anoptional chain transfer agent (CTA) and a boron containing NCA activatorrepresented by the formula (1) where: Z is (L-H) or a reducible Lewisacid; L is a neutral Lewis base (as further described above); H ishydrogen; (L-H) is a Bronsted acid (as further described above); A^(d−)is a boron containing non-coordinating anion having the charged (asfurther described above); d is 1, 2, or 3.

In an embodiment according to the invention in any of the NCA'srepresented by Formula 1 described above, the anion component A^(d−) isrepresented by the formula [M*^(k*+)Q*_(n*)]^(d*−) wherein k* is 1, 2,or 3; n* is 1, 2, 3, 4, 5, or 6 (or 1, 2, 3, or 4); n*−k*=d*; M* isboron; and Q* is independently selected from hydride, bridged orunbridged dialkylamido, halogen, alkoxide, aryloxide, hydrocarbylradicals, said Q* having up to 20 carbon atoms with the proviso that innot more than 1 occurrence is Q* a halogen.

This invention also relates in an embodiment of the invention to amethod to polymerize olefins comprising contacting olefins (such asethylene and/or propylene) with a long-bridged (e.g.,imino-phenylene-alkylene-imino bridged) salen catalyst compound asdescribed above, optionally with a CTA and an NCA activator representedby the Formula (2):R^(n)M**(ArNHal)_(4−n)  (2)where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. Typically the NCA comprising an anion of Formula 2also comprises a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Z_(d) ⁺ as described above.

In an embodiment according to the invention in any of the NCA'scomprising an anion represented by Formula 2 described above, R isselected from the group consisting of C₁ to C₃₀ hydrocarbyl radicals. Inan embodiment according to the invention, C₁ to C₃₀ hydrocarbyl radicalsmay be substituted with one or more C₁ to C₂₀ hydrocarbyl radicals,halide, hydrocarbyl substituted organometalloid, dialkylamido, alkoxy,aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, orother anionic substituent; fluoride; bulky alkoxides, where bulky meansC₄ to C₂₀ hydrocarbyl radicals; —SR^(a), —NR^(a) ₂, and —PR^(a) ₂, whereeach R^(a) is independently a C₄ to C₂₀ hydrocarbyl as defined above; ora C₄ to C₂₀ hydrocarbyl substituted organometalloid.

In an embodiment according to the invention in any of the NCA'scomprising an anion represented by Formula 2 described above, the NCAalso comprises cation comprising a reducible Lewis acid represented bythe formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl, or the reducible Lewis acidrepresented by the formula: (Ph₃C⁺), where Ph is phenyl or phenylsubstituted with one or more heteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In an embodiment according to the invention in any of the NCA'scomprising an anion represented by Formula 2 described above, the NCAmay also comprise a cation represented by the formula, (L-H)_(d) ⁺,wherein L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronstedacid; and d is 1, 2, or 3, or (L-H)_(d) ⁺ is a Bronsted acid selectedfrom ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.

Further examples of useful activators include those disclosed in U.S.Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporated byreference herein.

In an embodiment according to the invention, an activator useful hereincomprises a salt of a cationic oxidizing agent and a noncoordinating,compatible anion represented by the Formula (3):(OX^(e+))_(d)(A^(d−))_(e)  (3)wherein OX^(e+) is a cationic oxidizing agent having a charge of e+; eis 1, 2, or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anionhaving the charge of d− (as further described above). Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Suitable embodiments according to theinvention of A^(d−) include tetrakis(pentafluorophenyl)borate.

In an embodiment according to the invention, the long-bridged (e.g.,imino-phenylene-alkylene-imino bridged) salen catalyst compounds,optional CTA's, and/or NCA's described herein can be used with bulkyactivators. A “bulky activator” as used herein refers to anionicactivators represented by the formula:

where: each R¹ is, independently, a halide, or a fluoride; each R² is,independently, a halide, a C₆ to C₂₀ substituted aromatic hydrocarbylradical or a siloxy group of the formula —O—Si—R^(a), where R^(a) is aC₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl radical (or R² is a fluorideor a perfluorinated phenyl radical); each R³ is a halide, C₆ to C₂₀substituted aromatic hydrocarbyl radical or a siloxy group of theformula —O—Si—R^(a), where R^(a) is a C₁ to C₂₀ hydrocarbyl radical orhydrocarbylsilyl group (or R³ is a fluoride or a C₆ perfluorinatedaromatic hydrocarbyl radical); wherein R² and R³ can form one or moresaturated or unsaturated, substituted or unsubstituted rings (or R² andR³ form a perfluorinated phenyl ring); L is a neutral Lewis base; (L-H)⁺is a Bronsted acid; d is 1, 2, or 3; wherein the anion has a molecularweight of greater than 1020 g/mol; and wherein at least three of thesubstituents on the B atom each have a molecular volume of greater than250 cubic Å, or greater than 300 cubic Å, or greater than 500 cubic Å.

As discussed above, “Molecular volume” is used herein as anapproximation of spatial steric bulk of an activator molecule insolution. Exemplary bulky substituents of activators suitable herein andtheir respective scaled volumes and molecular volumes are shown in thetable below. The dashed bonds indicate binding to boron, as in thegeneral formula above.

Molecular Formula of MV Total Structure of boron each Per subst. MVActivator substituents substituent (Å³) (Å³) Dimethylaniliniumtetrakis(perfluoronaphthyl)borate

C₁₀F₇ 261 1044 Dimethylanilinium tetrakis(perfluorobiphenyl)borate

C₁₂F₉ 349 1396 [4-tButyl-PhNMe₂H] [(C₆F₃(C₆F₅)₂)₄B]

C₁₈F₁₃ 515 2060

Exemplary bulky activators useful in catalyst systems herein include:trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammoniumtetrakis (perfluoronaphthyl) borate, tripropylammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluoronaphthyl) borate, N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilyliumtetrakis(perfluoronaphthyl)borate,benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, triethylammoniumtetrakis(perfluorobiphenyl)borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilylium tetrakis(perfluorobiphenyl)borate, benzene (diazonium)tetrakis(perfluorobiphenyl)borate,[4-tert-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], and the types disclosed in U.S.Pat. No. 7,297,653, which is fully incorporated by reference herein.

Illustrative, but not limiting, examples of boron compounds which may beused as an activator in the processes according to the instantdisclosure include: trimethylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, tri(tert-butyl)ammoniumtetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate, tropilliumtetraphenyl borate, triphenylcarbenium tetraphenylborate,triphenylphosphonium tetraphenyl borate, triethylsilyliumtetraphenylborate, benzene(diazonium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammoniumtetrakis (pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, tropilliumtetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, triethylsilyliumtetrakis(pentafluorophenyl)borate,benzene(diazonium)tetrakis(pentafluorophenyl)borate, trimethylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethyl ammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammoniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,dimethyl(tert-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethyl aniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethyl anilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropilliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl) borate, triphenylphosphoniumtetrakis-(2,3,4,6-tetrafluoro phenyl)borate, triethyl silyliumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammoniumtetrakis(perfluoro naphthyl)borate, triethylammoniumtetrakis(perfluoronaphthyl)borate, tripropyl ammoniumtetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl) borate, tri(tert-butyl)ammoniumtetrakis(perfluoronaphthyl)borate, N,N-dimethyl aniliniumtetrakis(perfluoronaphthyl)borate, N,N-diethyl aniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl)borate, tropilliumtetrakis(perfluoronaphthyl) borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylphosphoniumtetrakis(perfluoronaphthyl)borate, triethylsilylium tetrakis(perfluoronaphthyl)borate, benzene(diazonium)tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate,triethylammoniumtetrakis(perfluorobiphenyl) borate, tripropylammoniumtetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammoniumtetrakis(perfluorobiphenyl)borate, tri(tert-butyl)ammoniumtetrakis(perfluorobiphenyl) borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-diethylaniliniumtetrakis(perfluorobiphenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate, tropilliumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylphosphoniumtetrakis(perfluorobiphenyl)borate, triethylsilyliumtetrakis(perfluorobiphenyl)borate, benzene(diazonium)tetrakis(perfluorobiphenyl)borate, trimethylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triethylammoniumtetrakis(3,5-bis (trifluoro methyl) phenyl)borate,tripropylammoniumtetrakis(3,5-bis (trifluoromethyl)phenyl) borate,tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,tri(tert-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl aniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropilliumtetrakis(3,5-bis(trifluoro methyl)phenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl) borate, triphenylphosphoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilyliumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and dialkyl ammoniumsalts, such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,and dicyclohexyl ammonium tetrakis(pentafluorophenyl)borate; andadditional tri-substituted phosphonium salts, such astri(o-tolyl)phosphonium tetrakis (pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Suitable activators include: N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoro methyl) phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl) borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄⁻]; 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;tetrakis(pentafluorophenyl)borate; and4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In an embodiment according to the invention, the activator comprises atriaryl carbonium (such as triphenylcarbenium tetraphenylborate,triphenylcarbenium tetrakis-(2,3,4,6-tetrafluoro phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis (trifluoromethyl)phenyl)borate).

In an embodiment according to the invention, the activator comprises oneor more of: trialkylammonium tetrakis(pentafluorophenyl)borate,N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate,N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate, trialkylammoniumtetrakis-(2,3,4,6-tetrafluoro phenyl) borate, N,N-dialkylaniliniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammoniumtetrakis(perfluoronaphthyl)borate, N,N-dialkylaniliniumtetrakis(perfluoronaphthyl)borate, trialkylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dialkylaniliniumtetrakis(perfluorobiphenyl) borate,trialkylammoniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl aniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate,N,N-dialkyl-(2,4,6-trimethyl anilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, where alkyl is methyl, ethyl, propyl,n-butyl, sec-butyl, or tert-butyl.

In an embodiment according to the invention, any of the activatorsdescribed herein may be mixed together before or after combination withthe catalyst compound and/or optional CTA and/or NCA, or before beingmixed with the catalyst compound and/or optional CTA, and/or NCA.

In an embodiment according to the invention two NCA activators may beused in the polymerization and the molar ratio of the first NCAactivator to the second NCA activator can be any ratio. In an embodimentaccording to the invention, the molar ratio of the first NCA activatorto the second NCA activator is 0.01:1 to 10,000:1, or 0.1:1 to 1000:1,or 1:1 to 100:1.

In an embodiment according to the invention, the NCAactivator-to-catalyst ratio is a 1:1 molar ratio, or 0.1:1 to 100:1, or0.5:1 to 200:1, or 1:1 to 500:1 or 1:1 to 1000:1. In an embodimentaccording to the invention, the NCA activator-to-catalyst ratio is 0.5:1to 10:1, or 1:1 to 5:1.

In an embodiment according to the invention, the catalyst compounds canbe combined with combinations of alumoxanes and NCA's (see for example,U.S. Pat. Nos. 5,153,157, 5,453,410, EP 0 573 120 B1, WO 9407928, and WO95/14044 which discuss the use of an alumoxane in combination with anionizing activator, all of which are incorporated by reference herein).

Useful chain transfer agents are typically alkylalumoxanes, a compoundrepresented by the formula AlR³, ZnR² (where each R is, independently, aC₁-C₈ aliphatic radical, preferably methyl, ethyl, propyl butyl, pentyl,hexyl octyl or an isomer thereof) or a combination thereof, such asdiethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum,trioctylaluminum, or a combination thereof.

Scavengers or Co-Activators

In an embodiment according to the invention the catalyst system mayfurther include scavengers and/or co-activators. Suitable aluminum alkylor organoaluminum compounds which may be utilized as scavengers orco-activators include, for example, trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike. Other oxophilic species such as diethyl zinc may be used.

Catalyst Supports

In an embodiment according to the invention, the catalyst system maycomprise an inert support material. In an embodiment according to theinvention, the support material comprises a porous support material, forexample, talc, and/or inorganic oxides. Other suitable support materialsinclude zeolites, clays, organoclays, or any other organic or inorganicsupport material and the like, or mixtures thereof.

In an embodiment according to the invention, the support material is aninorganic oxide in a finely divided form. Suitable inorganic oxidematerials for use in catalyst systems herein include Groups 2, 4, 13,and 14 metal oxides, such as silica, alumina, and mixtures thereof.Other inorganic oxides that may be employed either alone or incombination with the silica, and/or alumina include magnesia, titania,zirconia, montmorillonite, phyllosilicate, and/or the like. Othersuitable support materials include finely divided functionalizedpolyolefins, such as finely divided polyethylene.

In an embodiment according to the invention, the support material mayhave a surface area in the range of from about 10 to about 700 m²/g,pore volume in the range of from about 0.1 to about 4.0 cc/g and averageparticle size in the range of from about 5 to about 500 μm, or thesurface area of the support material is in the range of from about 50 toabout 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g andaverage particle size of from about 10 to about 200 μm. In an embodimentaccording to the invention, a majority portion of the surface area ofthe support material is in the range is from about 100 to about 400m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particlesize is from about 5 to about 100 μm. In an embodiment according to theinvention, the average pore size of the support material is in the rangeof from 10 to 1000 Å, or 50 to about 500 Å, or 75 to about 350 Å. In anembodiment according to the invention, the support material is a highsurface area, amorphous silica having a surface area greater than orequal to about 300 m²/g, and/or a pore volume of 1.65 cm³/g. Suitablesilicas are marketed under the trade names of Davison 952 or Davison 955by the Davison Chemical Division of W.R. Grace and Company. In anembodiment according to the invention the support may comprise Davison948.

In an embodiment according to the invention, the support material shouldbe essentially dry, that is, essentially free of absorbed water. Dryingof the support material can be effected by heating or calcining at about100° C. to about 1000° C., or at a temperature of at least about 400°C., or 500° C., or 600° C. When the support material is silica, it isheated to at least 200° C., or about 200° C. to about 850° C., or atleast 600° C. for a time of about 1 minute to about 100 hours, or fromabout 12 hours to about 72 hours, or from about 24 hours to about 60hours. In an embodiment according to the invention, the calcined supportmaterial must have at least some reactive hydroxyl (OH) groups toproduce supported catalyst systems according to the instant disclosure.

In an embodiment according to the invention, the calcined supportmaterial is contacted with at least one polymerization catalystcomprising at least one catalyst compound and an activator. In anembodiment according to the invention, the support material, havingreactive surface groups, typically hydroxyl groups, is slurried in anon-polar solvent and the resulting slurry is contacted with a solutionof a catalyst compound and an activator. In an embodiment according tothe invention, the slurry of the support material is first contactedwith the activator for a period of time in the range of from about 0.5hours to about 24 hours, or from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours. The solution of the catalystcompound is then contacted with the isolated supportactivator. In anembodiment according to the invention, the supported catalyst system isgenerated in situ. In alternate embodiments according to the invention,the slurry of the support material is first contacted with the catalystcompound for a period of time in the range of from about 0.5 hours toabout 24 hours, or from about 2 hours to about 16 hours, or from about 4hours to about 8 hours. The slurry of the supported catalyst compound isthen contacted with the activator solution.

In an embodiment according to the invention, the mixture of thecatalyst, activator and support is heated to about 0° C. to about 70°C., or to about 23° C. to about 60° C., or to 25° C. (room temperature).Contact times typically range from about 0.5 hours to about 24 hours, orfrom about 2 hours to about 16 hours, or from about 4 hours to about 8hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator and the catalyst compound are at leastpartially soluble and which are liquid at reaction temperatures.Suitable non-polar solvents include alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

Polymerization Processes

In an embodiment according to the invention, a polymerization processesincludes contacting monomers (such as ethylene and propylene), andoptionally comonomers, with a catalyst system comprising an activatorand at least one catalyst compound, as described above. In an embodimentaccording to the invention, the catalyst compound and activator may becombined in any order, and may be combined prior to contacting with themonomer. In an embodiment according to the invention, the catalystcompound and/or the activator are combined after contacting with themonomer.

In an embodiment according to the invention, the salen ligand may becombined with the metalation reagent to produce the metal substitutedcatalyst precursor prior to catalyst activation, with or withoutisolation of the catalyst precursor, or simultaneously with activationand/or in the presence of monomers such that the catalyst is formedin-situ during the polymerization process.

In an embodiment according to the invention, a process to polymerizeolefins may comprise: contacting a salen ligand with a metalationreagent to produce a catalyst precursor; and contacting the catalystprecursor with an activator and one or more olefins at polymerizationconditions to produce a polyolefin; wherein the salen ligand isrepresented by the formula:

wherein the metalation reagent is represented by the formula: MX¹X²X³X⁴

wherein the catalyst precursor is represented by the formula:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; wherein n is 1 or 2; wherein M is a Group 3, 4,5 or 6 transition metal, provided however where n is 1 then X² is notpresent; wherein N¹ and N² are nitrogen and O¹ and O² are oxygen;wherein each of X¹ and X² (where present) is, independently, a univalentC₁ to C₂₀ hydrocarbyl radical, a functional group comprising elementsfrom Groups 13-17 of the periodic table of the elements, or X¹ and X² ifpresent may join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; wherein Y comprises an sp³ carbon directly bonded to N² andis selected from the group consisting of divalent C₁ to C₄₀ hydrocarbylradicals, divalent functional groups comprising elements from Groups13-17 of the periodic table of the elements, and combinations thereof;and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, andR¹² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R¹² may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure.

In a particular embodiment according to the invention, a process topolymerize olefins may comprise: contacting a salen ligand with ametalation reagent to produce a catalyst precursor; and contacting thecatalyst precursor with an activator and one or more olefins atpolymerization conditions to produce a polyolefin; wherein the salenligand is represented by the formula:

wherein the metalation reagent is represented by the formula: MX¹X²X³X⁴

wherein the catalyst precursor is represented by the formula:

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen, and comprising[O¹,N¹,N²]13 [N¹,N²,O²] in a fac-mer arrangement, a mer-fac arrangementor a fac-fac arrangement; or wherein activation rearranges[O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement, a mer-fac arrangementor a fac-fac arrangement; wherein each solid line represents a covalentbond and each dashed line represents a bond having varying degrees ofcovalency and a varying degree of coordination; wherein M is a Group 4,5 or 6 transition metal; wherein each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; wherein Y comprises an sp³ carbon directly bonded to N² andis selected from the group consisting of divalent C₁ to C₄₀ hydrocarbylradicals, divalent functional groups comprising elements from Groups13-17 of the periodic table of the elements, and combinations thereof;and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, andR¹² is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R¹² may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure.

In an embodiment according to the invention, the salen ligand and themetalation reagent may be contacted prior to combination with theactivator and subsequently with the activator without isolation of theprecursor catalyst compound. In an embodiment according to theinvention, the salen ligand and the metalation reagent may be contactedin the presence of the activator, in the presence of one or moreolefins, or a combination thereof, e.g., in an in-situ polymerizationprocess.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, or C₂ to C₂₀ alpha olefins, or C₂ to C₁₂ alpha olefins,or ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene and isomers thereof. In an embodimentaccording to the invention, the monomer comprises propylene and anoptional comonomers comprising one or more ethylene or C₄ to C₄₀olefins, or C₄ to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₄ to C₄₀olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups. Inan embodiment according to the invention, the monomer comprises ethyleneor ethylene and a comonomer comprising one or more C₃ to C₄₀ olefins, orC₄ to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomersmay be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclo do decene, 7-ox anorbornene, 7-ox anorbornadiene,substituted derivatives thereof, and isomers thereof, or hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, ornorbornene, norbornadiene, and dicyclopentadiene.

In an embodiment according to the invention one or more dienes arepresent in the polymer produced herein at up to 10 weight %, or at0.00001 to 1.0 weight %, or 0.002 to 0.5 weight %, or 0.003 to 0.2weight %, based upon the total weight of the composition. In anembodiment according to the invention 500 ppm or less of diene is addedto the polymerization, or 400 ppm or less, or 300 ppm or less. In anembodiment according to the invention at least 50 ppm of diene is addedto the polymerization, or 100 ppm or more, or 150 ppm or more.

Diolefin monomers useful in this invention include any hydrocarbonstructure, or C₄ to C₃₀, having at least two unsaturated bonds, whereinat least two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).In an embodiment according to the invention, the diolefin monomers maybe selected from alpha, omega-diene monomers (i.e. di-vinyl monomers).More or, the diolefin monomers are linear di-vinyl monomers, most orthose containing from 4 to 30 carbon atoms. Examples of dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and lowmolecular weight polybutadienes (Mw less than 1000 g/mol). Cyclic dienesinclude cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene or higher ring containingdiolefins with or without substituents at various ring positions.

In an embodiment according to the invention, where butene is thecomonomer, the butene source may be a mixed butene stream comprisingvarious isomers of butene. The 1-butene monomers are expected to bepreferentially consumed by the polymerization process. Use of such mixedbutene streams will provide an economic benefit, as these mixed streamsare often waste streams from refining processes, for example, C₄raffinate streams, and can therefore be substantially less expensivethan pure 1-butene.

Polymerization processes according to the instant disclosure may becarried out in any manner known in the art. Any suspension, homogeneous,bulk, solution, slurry, or gas phase polymerization process known in theart can be used. Such processes can be run in a batch, semi-batch, orcontinuous mode. Homogeneous polymerization processes and slurryprocesses are suitable for use herein, wherein a homogeneouspolymerization process is defined to be a process where at least 90 wt %of the product is soluble in the reaction media. A bulk homogeneousprocess is suitable for use herein, wherein a bulk process is defined tobe a process where monomer concentration in all feeds to the reactor is70 volume % or more. In an embodiment according to the invention, nosolvent or diluent is present or added in the reaction medium, (exceptfor the small amounts used as the carrier for the catalyst system orother additives, or amounts typically found with the monomer; e.g.,propane in propylene). In an embodiment according to the invention, theprocess is a slurry process. As used herein the term “slurrypolymerization process” means a polymerization process where a supportedcatalyst is employed and monomers are polymerized on the supportedcatalyst particles. At least 95 wt % of polymer products derived fromthe supported catalyst are in granular form as solid particles (notdissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In an embodiment according to theinvention, aliphatic hydrocarbon solvents are used as the solvent, suchas isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In an embodiment according tothe invention, the solvent is not aromatic, or aromatics are present inthe solvent at less than 1 wt %, or less than 0.5 wt %, or less than 0.0wt % based upon the weight of the solvents.

In an embodiment according to the invention, the feed concentration ofthe monomers and comonomers for the polymerization is 60 vol % solventor less, or 40 vol % or less, or 20 vol % or less, based on the totalvolume of the feedstream. Or the polymerization is run in a bulkprocess.

Polymerizations can be run at any temperature and/or pressure suitableto obtain the desired ethylene polymers. Suitable temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., or about 20° C. to about 200° C., or about 35° C. toabout 150° C., or from about 40° C. to about 120° C., or from about 45°C. to about 80° C.; and at a pressure in the range of from about 0.35MPa to about 10 MPa, or from about 0.45 MPa to about 6 MPa, or fromabout 0.5 MPa to about 4 MPa. In an embodiment according to theinvention, the run time of the reaction is from about 0.1 minutes toabout 24 hours, or up to 16 hours, or in the range of from about 5 to250 minutes, or from about 10 to 120 minutes.

In an embodiment according to the invention, hydrogen is present in thepolymerization reactor at a partial pressure of 0.001 to 50 psig (0.007to 345 kPa), or from 0.01 to 25 psig (0.07 to 172 kPa), or 0.1 to 10psig (0.7 to 70 kPa).

In an embodiment according to the invention, the activity of thecatalyst is at least 50 g/mmol/hr, or 500 or more g/mmol/hr, or 5000 ormore g/mmol/hr, or 50,000 or more mmol/hr. In an alternate embodimentaccording to the invention, the conversion of olefin monomer is at least10%, based upon polymer yield and the weight of the monomer entering thereaction zone, or 20% or more, or 30% or more, or 50% or more, or 80% ormore.

In an embodiment according to the invention, the polymerizationconditions include one or more of the following: 1) temperatures of 0 to300° C. (or 25 to 150° C., or 40 to 120° C., or 45 to 80° C.); 2) apressure of atmospheric pressure to 10 MPa (or 0.35 to 10 MPa, or from0.45 to 6 MPa, or from 0.5 to 4 MPa); 3) the presence of an aliphatichydrocarbon solvent (such as isobutane, butane, pentane, isopentane,hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof;cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; or wherearomatics are or present in the solvent at less than 1 wt %, or lessthan 0.5 wt %, or at 0 wt % based upon the weight of the solvents); 4)wherein the catalyst system used in the polymerization comprises lessthan 0.5 mol %, or 0 mol % alumoxane, or the alumoxane is present at amolar ratio of aluminum to transition metal less than 500:1, or lessthan 300:1, or less than 100:1, or less than 1:1; 5) the polymerizationor occurs in one reaction zone; 6) the productivity of the catalystcompound is at least 80,000 g/mmol/hr (or at least 150,000 g/mmol/hr, orat least 200,000 g/mmol/hr, or at least 250,000 g/mmol/hr, or at least300,000 g/mmol/hr); 7) scavengers (such as trialkyl aluminum compounds)are absent (e.g., present at zero mol %) or the scavenger is present ata molar ratio of scavenger to transition metal of less than 100:1, orless than 50:1, or less than 15:1, or less than 10:1; and/or 8)optionally hydrogen is present in the polymerization reactor at apartial pressure of 0.007 to 345 kPa (0.001 to 50 psig) (or from 0.07 to172 kPa (0.01 to 25 psig), or 0.7 to 70 kPa (0.1 to 10 psig)).

In an embodiment according to the invention, the catalyst system used inthe polymerization comprises no more than one catalyst compound. A“reaction zone” also referred to as a “polymerization zone” is a vesselwhere polymerization takes place, for example a batch reactor. Whenmultiple reactors are used in either series or parallel configuration,each reactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In an embodiment according to the invention, thepolymerization occurs in one reaction zone.

In an embodiment according to the invention, a process to polymerizeolefins comprises contacting one or more olefins with a catalyst systemaccording to any one or combination of embodiments according to theinvention disclosed herein at polymerization conditions to produce apolyolefin.

In a particular embodiment according to the invention, thepolymerization conditions comprise a temperature of from about 0° C. toabout 300° C., a pressure from about 0.35 MPa to about 10 MPa, and atime from about 0.1 minutes to about 24 hours. In an embodimentaccording to the invention, the one or more olefins comprise propylene.In an embodiment according to the invention, the polyolefin comprises atleast 50 mole % propylene.

In an embodiment according to the invention, a process to polymerizeolefins comprises contacting one or more olefins with a catalyst systemat polymerization conditions to produce a polyolefin, the catalystsystem comprising an activator and a catalyst compound represented bythe formula:

wherein M is a Group 3, 4, 5 or 6 transition metal; wherein N¹ and N²are nitrogen and O¹ and O² are oxygen; wherein n is 1 or 2; wherein eachX is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or where n is 2 then each X may join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure; wherein Ycomprises an sp³ carbon directly bonded to N² and is selected from thegroup consisting of divalent C₁ to C₄₀ hydrocarbyl radicals, divalentfunctional groups comprising elements from Groups 13-17 of the periodictable of the elements, and combinations thereof; and wherein each of R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is, independently, ahydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group comprisingelements from Group 13-17 of the periodic table of the elements, or twoor more of R¹ to R¹² may independently join together to form a C₄ to C₆₂cyclic or polycyclic ring structure.

In a particular embodiment according to the invention, a process topolymerize olefins comprises contacting one or more olefins with acatalyst system at polymerization conditions to produce a polyolefin,the catalyst system comprising an activator and a catalyst compoundrepresented by the formula:

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen and comprising[O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-fac arrangementor a fac-fac arrangement, or wherein activation rearranges[O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement or a mer-facarrangement or a fac-fac arrangement; wherein each solid line representsa covalent bond and each dashed line represents a bond having varyingdegrees of covalency and a varying degree of coordination; wherein M isa Group 3, 4, 5 or 6 transition metal; wherein each of X¹ and X² is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or X¹ and X² join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; wherein Y comprises an sp³ carbon directlybonded to N² and is selected from the group consisting of divalent C₁ toC₄₀ hydrocarbyl radicals, divalent functional groups comprising elementsfrom Groups 13-17 of the periodic table of the elements, andcombinations thereof; and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or two or more of R¹ to R¹²may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure.

In an embodiment according to the invention, the polymerizationconditions comprise a temperature of from about 0° C. to about 300° C.,a pressure from about 0.35 MPa to about 10 MPa, and a time from about0.1 minutes to about 24 hours.

In an embodiment according to the invention, two or more differentcatalyst compounds are present in the catalyst system used herein. In anembodiment according to the invention, two or more different catalystcompounds are present in the reaction zone where the process(es)described herein occur. When two transition metal compound basedcatalysts are used in one reactor as a mixed catalyst system, the twotransition metal compounds are chosen such that the two are preferablycompatible. Compatible catalysts are those catalysts having similarkinetics of termination and insertion of monomer and comonomer(s) and/ordo not detrimentally interact with each other. For purposes herein, theterm “incompatible catalysts” refers to and means catalysts that satisfyone or more of the following: 1) those catalysts that when presenttogether reduce the activity of at least one of the catalysts by greaterthan 50%; 2) those catalysts that under the same reactive conditionsproduce polymers such that one of the polymers has a molecular weightthat is more than twice the molecular weight of the other polymer; and3) those catalysts that differ in comonomer incorporation or reactivityratio under the same conditions by more than about 30%. A simplescreening method such as by ¹H or ¹³C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible. In an embodiment according to the invention,the catalyst systems use the same activator for the catalyst compounds.In an embodiment according to the invention, two or more differentactivators, such as a non-coordinating anion activator and an alumoxane,can be used in combination. If one or more catalyst compounds contain anX¹ or X² ligand which is not a hydride, or a hydrocarbyl, then in anembodiment according to the invention the alumoxane is contacted withthe catalyst compounds prior to addition of the non-coordinating anionactivator.

In an embodiment according to the invention, when two transition metalcompounds (pre-catalysts) are utilized, they may be used in any ratio.In an embodiment according to the invention, a molar ratio of a firsttransition metal compound (A) to a second transition metal compound (B)will fall within the range of (A:B) 1:1000 to 1000:1, or 1:100 to 500:1,or 1:10 to 200:1, or 1:1 to 100:1, or 1:1 to 75:1, or 5:1 to 50:1. Theparticular ratio chosen will depend on the exact pre-catalysts chosen,the method of activation, and the end product desired. In an embodimentaccording to the invention, when using two pre-catalysts, where both areactivated with the same activator, useful mole percents, based upon thetotal moles of the pre-catalysts, are 10:90 to 0.1:99, or 25:75 to 99:1,or 50:50 to 99.5:0.5, or 50:50 to 99:1, or 75:25 to 99:1, or 90:10 to99:1.

Polyolefin Products

The instant disclosure also relates to compositions of matter producedby the methods described herein.

In an embodiment according to the invention, the process describedherein produces propylene homopolymers or propylene copolymers, such aspropylene-ethylene and/or propylene-α-olefin (or C₃ to C₂₀) copolymers(such as propylene-hexene copolymers or propylene-octene copolymers)having an Mw/Mn of greater than 1 to 4 (or greater than 1 to 3).

Likewise, the process of this invention produces olefin polymers, orpolyethylene and polypropylene homopolymers and copolymers. In anembodiment according to the invention, the polymers produced herein arehomopolymers of ethylene or propylene, are copolymers of ethylene orhaving from 0 to 25 mole % (or from 0.5 to 20 mole %, or from 1 to 15mole %, or from 3 to 10 mole %) of one or more C₃ to C₂₀ olefincomonomer (or C₃ to C₁₂ alpha-olefin, or propylene, butene, hexene,octene, decene, dodecene, or propylene, butene, hexene, octene), or arecopolymers of propylene or having from 0 to 25 mole % (or from 0.5 to 20mole %, or from 1 to 15 mole %, or from 3 to 10 mole %) of one or moreof C₂ or C₄ to C₂₀ olefin comonomer (or ethylene or C₄ to C₁₂alpha-olefin, or ethylene, butene, hexene, octene, decene, dodecene, orethylene, butene, hexene, octene).

In an embodiment according to the invention, the polymers producedherein have an Mw of 5,000 to 1,000,000 g/mol (e.g., 25,000 to 750,000g/mol, or 50,000 to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to40, or 1.2 to 20, or 1.3 to 10, or 1.4 to 5, or 1.5 to 4, or 1.5 to 3.

In an embodiment according to the invention, the polymer produced hereinhas a unimodal or multimodal molecular weight distribution as determinedby Gel Permeation Chromatography (GPC). By “unimodal” is meant that theGPC trace has one peak or inflection point. By “multimodal” is meantthat the GPC trace has at least two peaks or inflection points. Aninflection point is that point where the second derivative of the curvechanges in sign (e.g., from negative to positive or vice versa).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC asdescribed in US 20060173123 page 24-25, paragraphs [0334] to [0341].

In an embodiment according to the invention, one or more olefinscomprise propylene. In a particular embodiment, the polyolefin comprisesat least 50 mole % propylene, preferably at least 75 mol % propylene,preferably at least 85 mol % propylene. In an embodiment according tothe invention, the polyolefin has a concentration of meso isotacticpentads [mmmm] of greater than or equal to about 50 wt %, or 60 wt %, or70 wt %, or 80 wt %, or 90 wt %, or greater than or equal to about 99 wt%, based on the total weight of the polymer. In a particular embodiment,the polyolefin comprises at least 50 mole % propylene having aconcentration of meso isotactic pentads [mmmm] of greater than or equalto about 90 wt %, based on the total weight of the polymer. In anembodiment according to the invention, the polyolefin has aconcentration of meso isotactic pentads [mmmm] of greater than or equalto about 50 wt %, or 60 wt %, or 70 wt %, or 80 wt %, or 90 wt %, orgreater than or equal to about 99 wt %, based on the total weight of thepolymer as determined by ¹³C NMR. The polypropylene polymer preferablyhas some level of isotacticity and is preferably isotactic polypropyleneor highly isotactic polypropylene. As used herein, “isotactic” isdefined as having at least 10% isotactic pentads according to analysisby ¹³C NMR. As used herein, “highly isotactic” is defined as having atleast 60% isotactic pentads according to analysis by ¹³C NMR.

The polypropylene polymer can have a propylene meso diads content of 90%or more, 92% or more, 94% or more, 95% or more, 96% or more, 97% ormore, or 98% or more. The isotacticity of the polypropylene polymer canbe measured by ¹³C NMR. For example, suitable techniques for measuringthe isotacticity of the polypropylene polymer can be as discussed anddescribed in U.S. Pat. No. 4,950,720. Expressed another way, theisotacticity of the polypropylene polymer, as measured by ¹³C NMR, andexpressed as pentad content, is greater than 93% or 95%, or 97% incertain embodiments.

The polymer produced herein can have a heat of fusion (H_(f), DSC secondheat) from a high of 50 J/g or more, preferably 60 J/g or more,preferably 70 J/g or more, preferably 80 J/g or more, preferably 90 J/gor more, preferably about 95 J/g or more, or preferably about 100 J/g ormore.

In an embodiment according to the invention, the polyolefin comprises atleast 50 mole % propylene, e.g., isotactic polypropylene, and has amelting point (T_(melt) or Tm) determined using differential scanningcalorimetry, greater than 154° C., e.g., from about 145° C. to about175° C., or from about 145° C. to about 170° C. Within this range, in anembodiment according to the invention, the polyolefin has a meltingpoint T_(melt) of greater than or equal to about 148° C., or greaterthan or equal to about 150° C., or greater than or equal to about 152°C., or greater than or equal to about 154° C., or greater than or equalto about 155° C., or greater than or equal to about 156° C., or greaterthan or equal to about 157° C., or greater than or equal to about 158°C., or greater than or equal to about 159° C., or greater than or equalto about 160° C., or greater than or equal to about 161° C., or greaterthan or equal to about 162° C., or greater than or equal to about 163°C., or greater than or equal to about 164° C., or greater than or equalto about 165° C. In embodiments, the polyolefin has a melting pointT_(melt) of less than or equal to about 175° C., or less than or equalto about 170° C., or less than or equal to about 167° C. In embodiments,the polyolefin comprises greater than 95 wt % isotactic polypropylene,or greater than 96 wt % isotactic polypropylene, or greater than 97 wt %isotactic polypropylene, or greater than 98 wt % isotacticpolypropylene, up to 99.9 wt % isotactic polypropylene, by weight of thepolyolefin. In particular embodiments, the polyolefin comprises greaterthan 95 wt % isotactic polypropylene and has a melting point greaterthan or equal to about 160° C., or wherein the polyolefin comprisesgreater than 98 wt % isotactic polypropylene and has a melting pointgreater than or equal to about 165° C.

Blends

In an embodiment according to the invention, the polymer (or thepolyethylene or polypropylene) produced herein is combined with one ormore additional polymers prior to being formed into a film, molded partor other article. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, polyesters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In an embodiment according to the invention, the polymer (or thepolyethylene or polypropylene) is present in the above blends, at from10 to 99 wt %, based upon the weight of the polymers in the blend, or 20to 95 wt %, or at least 30 to 90 wt %, or at least 40 to 90 wt %, or atleast 50 to 90 wt %, or at least 60 to 90 wt %, or at least 70 to 90 wt%.

The blends described above may be produced by mixing the polymersaccording to the invention with one or more polymers (as describedabove), by connecting reactors together in series to make reactor blendsor by using more than one catalyst in the same reactor to producemultiple species of polymer. The polymers can be mixed together prior tobeing put into the extruder or may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g.,IRGAFOS 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

In an embodiment according to the invention, any of the foregoingpolymers, such as the foregoing polypropylenes or blends thereof, may beused in a variety of end-use applications. Applications include, forexample, mono- or multi-layer blown, extruded, and/or shrink films.These films may be formed by any number of well-known extrusion orcoextrusion techniques, such as a blown bubble film processingtechnique, wherein the composition can be extruded in a molten statethrough an annular die and then expanded to form a uni-axial or biaxialorientation melt prior to being cooled to form a tubular, blown film,which can then be axially slit and unfolded to form a flat film. Filmsmay be subsequently unoriented, uniaxially oriented, or biaxiallyoriented to the same or different extents. One or more of the layers ofthe film may be oriented in the transverse and/or longitudinaldirections to the same or different extents. The uniaxial orientationcan be accomplished using typical cold drawing or hot drawing methods.Biaxial orientation can be accomplished using tenter frame equipment ora double bubble processes and may occur before or after the individuallayers are brought together. For example, a polyethylene layer can beextrusion coated or laminated onto an oriented polypropylene layer orthe polyethylene and polypropylene can be coextruded together into afilm then oriented. Likewise, oriented polypropylene could be laminatedto oriented polyethylene or oriented polyethylene could be coated ontopolypropylene then optionally the combination could be oriented evenfurther. Typically the films are oriented in the machine direction (MD)at a ratio of up to 15, or between 5 and 7, and in the transversedirection (TD) at a ratio of up to 15, or 7 to 9. However, in anembodiment according to the invention the film is oriented to the sameextent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In an embodiment according to the invention, one or more layers may bemodified by corona treatment, electron beam irradiation, gammairradiation, flame treatment, or microwave. In an embodiment accordingto the invention, one or both of the surface layers is modified bycorona treatment.

Molded Products

The compositions described herein (particularly polypropylenecompositions) may also be used to prepare molded products in any moldingprocess, including but not limited to, injection molding, gas-assistedinjection molding, extrusion blow molding, injection blow molding,injection stretch blow molding, compression molding, rotational molding,foam molding, thermoforming, sheet extrusion, and profile extrusion. Themolding processes are well known to those of ordinary skill in the art.

Further, the compositions described herein (particularly polypropylenecompositions) may be shaped into desirable end use articles by anysuitable means known in the art. Thermoforming, vacuum forming, blowmolding, rotational molding, slush molding, transfer molding, wet lay-upor contact molding, cast molding, cold forming matched-die molding,injection molding, spray techniques, profile co-extrusion, orcombinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Typically, an extrudate film of the composition ofthis invention (and any other layers or materials) is placed on ashuttle rack to hold it during heating. The shuttle rack indexes intothe oven which pre-heats the film before forming. Once the film isheated, the shuttle rack indexes back to the forming tool. The film isthen vacuumed onto the forming tool to hold it in place and the formingtool is closed. The tool stays closed to cool the film and the tool isthen opened. The shaped laminate is then removed from the tool. Thethermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution.

Blow molding is another suitable forming means for use with thecompositions of this invention, which includes injection blow molding,multi-layer blow molding, extrusion blow molding, and stretch blowmolding, and is especially suitable for substantially closed or hollowobjects, such as, for example, gas tanks and other fluid containers.Blow molding is described in more detail in, for example, CONCISEENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I.Kroschwitz, ed., John Wiley & Sons 1990).

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheets may be made either byextruding a substantially flat profile from a die, onto a chill roll, orby calendaring. Sheets are generally considered to have a thickness offrom 254 μm to 2540 μm (10 mils to 100 mils), although any given sheetmay be substantially thicker.

Non-Wovens and Fibers

The polyolefin compositions described above may also be used to preparenonwoven fabrics and fibers of this invention in any nonwoven fabric andfiber making process, including but not limited to, melt blowing,spunbonding, film aperturing, and staple fiber carding. A continuousfilament process may also be used. Or a spunbonding process is used. Thespunbonding process is well known in the art. Generally it involves theextrusion of fibers through a spinneret. These fibers are then drawnusing high velocity air and laid on an endless belt. A calendar roll isgenerally then used to heat the web and bond the fibers to one anotheralthough other techniques may be used such as sonic bonding and adhesivebonding.

Embodiments

Accordingly, the instant disclosure relates to the followingembodiments:

-   E1. A catalyst compound represented by the formula:

-   -   wherein M is a Group 3, 4, 5 or 6 transition metal; wherein N¹        and N² are nitrogen and O¹ and O² are oxygen; wherein n is 1 or        2; wherein each X is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or where n        is 2 then each X may join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure; wherein Y comprises an sp³ carbon        directly bonded to N² and is selected from the group consisting        of divalent C₁ to C₄₀ hydrocarbyl radicals, divalent functional        groups comprising elements from Groups 13-17 of the periodic        table of the elements, and combinations thereof and wherein each        of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is,        independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a        functional group comprising elements from Group 13-17 of the        periodic table of the elements, or two or more of R¹ to R¹² may        independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure.

-   E2. The catalyst compound according to Embodiment E1, wherein the    compound is represented by the formula:

-   wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴,    R¹⁵, and R¹⁶ is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl    radical, a functional group comprising elements from Group 13-17 of    the periodic table of the elements, or two or more of R¹ to R¹⁰ and    R¹³ to R¹⁶ may independently join together to form a C₄ to C₆₂    cyclic or polycyclic ring structure.-   E3. The catalyst compound according to Embodiment E1, wherein the    compound is represented by the formula:

-   wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is, independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R¹⁰ and R¹³ to R¹⁸ may independently join together to form a    C₄ to C₆₂ cyclic or polycyclic ring structure.-   E4. A catalyst compound represented by the formula:

-   wherein each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination; wherein M is a Group 4, 5 or 6    transition metal; wherein N¹ and N² are nitrogen and O¹ and O² are    oxygen; wherein each of X¹ and X² is, independently, a univalent C₁    to C₂₀ hydrocarbyl radical, a functional group comprising elements    from Groups 13-17 of the periodic table of the elements, or X¹ and    X² join together to form a C₄ to C₆₂ cyclic or polycyclic ring    structure; wherein Y comprises an sp³ carbon directly bonded to N²    and is selected from the group consisting of divalent C₁ to C₄₀    hydrocarbyl radicals, divalent functional groups comprising elements    from Groups 13-17 of the periodic table of the elements, and    combinations thereof; wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷,    R⁸, R⁹, R¹⁰, R¹¹ and R¹² is independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R¹² may independently join together to form a C₄ to C₆₂ cyclic    or polycyclic ring structure.-   E5. The catalyst compound according to any one of Embodiments E1 to    E4, wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-mer arrangement.-   E6. The catalyst compound according to any one of Embodiments E1 to    E4, wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a mer-fac arrangement.-   E7. The catalyst compound according to any one of Embodiments E1 to    E4, wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-fac arrangement.-   E8. The catalyst compound according to any one of Embodiments E1 to    E7, wherein M is Ti, Hf or Zr.-   E9. The catalyst compound according to any one of Embodiments E1 to    E8, wherein M is Hf.-   E10. The catalyst compound according to any one of Embodiments E1 to    E9, wherein each X (including each of X¹ and X²) is a benzyl    radical, a halogen radical, an O-i-propyl radical or an O-tert-butyl    radical.-   E11. The catalyst compound according to any one of Embodiments E1 to    E10, wherein each X (including each of X¹ and X²) is a benzyl    radical.-   E12. The catalyst compound according to any one of Embodiments E1 to    E11, wherein each of R¹ to R¹⁸ (if present) is, independently,    hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical.-   E13. The catalyst compound according to any one of Embodiments E1 to    E11, wherein each of R¹ to R¹⁸ (if present) is, independently,    hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbyl radical.-   E14. The catalyst compound according to any one of Embodiments E1 to    E13, wherein the sp3 carbon directly bonded to N² is a benzylic    carbon.-   E15. The catalyst compound according to any one of Embodiments E1 to    E14, wherein Y (if present) is a divalent aliphatic radical having    from 1 to 10 carbon atoms.-   E16. The catalyst compound according to any one of Embodiments E1 to    E15, wherein R¹¹ and R¹² (if present) join to form a phenylene ring    directly bonded to N² and Y, wherein the catalyst compound is    represented by the formula:

-   wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴,    R¹⁵, and R¹⁶ is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl    radical, a functional group comprising elements from Group 13-17 of    the periodic table of the elements, or two or more of R¹ to R¹⁰ and    R¹³ to R¹⁶ may independently join together to form a C₄ to C₆₂    cyclic or polycyclic ring structure.-   E17. The catalyst compound according to any one of Embodiments E1 to    E16, represented by the formula:

-   wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R¹⁰ and R¹³ to R¹⁸ may independently join together to form a    C₄ to C₆₂ cyclic or polycyclic ring structure; and/or    -   wherein R¹⁴ and R¹⁵ join to form a 2,3-naphthalenylene ring        directly bonded to N² and Y to form an        imino-naphthalenylene-alkylene-imino bridged salen compound,        represented by the formula:

-   wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁶,    R¹⁹, R²⁰, R²¹, and R²² is, independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R¹⁰ and R¹³ to R¹⁶ may independently join together to form a    C₄ to C₆₂ cyclic or polycyclic ring structure, and/or wherein the    naphthalenylene ring further comprises at least one additional    conjugated phenylene ring. E18. The catalyst compound according to    any one of Embodiments E1 to E17, wherein: each X including X¹ and    X² if present are benzyl radicals; at least one of R¹, R², R⁴, R⁵,    R⁷, and R⁸ are independently selected from the group consisting of:    C₁-C₁₀ alkyl, C₁-C₁₀ cycloalkyl, C₁-C₁₀ alkenyl C₁-C₁₀ alkoxy, aryl    substituted C₁-C₁₀ alkyl, C₁-C₁₀ aryl, halo, and combinations    thereof; and R³, R⁶, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ (if    present) are hydrogen.-   E19. The catalyst compound according to any one of Embodiments E1 to    E18, wherein at least one of R¹, R², R⁴, R⁵, R⁷, and R⁸ are    independently selected from the group consisting of: methyl, ethyl,    isopropyl, isobutyl, tertiary-butyl, isopentyl,    2-methyl-2-phenylethyl; methoxy, benzyl, adamantyl, chloro, bromo,    iodo, and combinations thereof.-   E20. The catalyst compound according to any one of Embodiments E1 to    E19, wherein R² and R⁴ are identical, R⁵ and R⁷ are identical, or a    combination thereof.-   E21. A catalyst system comprising an activator and a catalyst    compound according to any one of Embodiments E1 to E20.-   E22. A catalyst system comprising an activator and a catalyst    compound represented by the formula:

-   wherein each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination; wherein M is a Group 3, 4, 5 or 6    transition metal; wherein N¹ and N² are nitrogen and O¹ and O² are    oxygen; wherein each of X¹ and X² is, independently, a univalent C₁    to C₂₀ hydrocarbyl radical, a functional group comprising elements    from Groups 13-17 of the periodic table of the elements, or X¹ and    X² join together to form a C₄ to C₆₂ cyclic or polycyclic ring    structure, provided however where M is trivalent X² is not present;    wherein Y comprises an sp³ carbon directly bonded to N² and is    selected from the group consisting of divalent C₁ to C₄₀ hydrocarbyl    radicals, divalent functional groups comprising elements from Groups    13-17 of the periodic table of the elements, and combinations    thereof; wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,    R¹¹, and R¹² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl    radical, a functional group comprising elements from Group 13-17 of    the periodic table of the elements, or two or more of R¹ to R¹² may    independently join together to form a C₄ to C₆₂ cyclic or polycyclic    ring structure.-   E23. The catalyst system according to Embodiment E21 or Embodiment    E22 wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-mer arrangement.-   E24. The catalyst system according to Embodiment E21 or Embodiment    E22 wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a mer-fac arrangement.-   E25. The catalyst system according to Embodiment E21 or Embodiment    E22 wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-fac arrangement.-   E26. The catalyst system according to Embodiment E21 or Embodiment    E22 wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a    fac-mer arrangement.-   E27. The catalyst system according to Embodiment E21 or Embodiment    E22 wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a    mer-fac arrangement.-   E28. The catalyst system according to Embodiment E21 or Embodiment    E22 wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a    fac-fac arrangement.-   E29. The catalyst system according to any one of Embodiments E21 to    E28, wherein the activator comprises alumoxane, a non-coordinating    anion activator, or a combination thereof.-   E30. The catalyst system according to any one of Embodiments E21 to    E29, wherein the activator comprises alumoxane and the alumoxane is    present at a ratio of 1 mole aluminum or more per mole of catalyst    compound.-   E31. The catalyst system according to any one of Embodiments E21 to    E30, wherein the activator is represented by the formula:    (Z)_(d) ⁺(A^(d−))-   wherein Z is (L-H), or a reducible Lewis Acid, wherein L is a    neutral Lewis base, H is hydrogen and (L-H)⁺ is a Bronsted acid;    wherein A^(d−) is a non-coordinating anion having the charge d⁻; and    d is an integer from 1 to 3.-   E32. The catalyst system according to any one of Embodiments E21 to    E31, wherein the activator is represented by the formula:    (Z)_(d) ⁺(A^(d−))-   wherein A^(d−) is a non-coordinating anion having the charge d⁻;    wherein d is an integer from 1 to 3, and wherein Z is a reducible    Lewis acid represented by the formula: (Ar₃C⁺), where Ar is aryl    radical, an aryl radical substituted with a heteroatom, an aryl    radical substituted with one or more C₁ to C₄₀ hydrocarbyl radicals,    an aryl radical substituted with one or more functional groups    comprising elements from Groups 13-17 of the periodic table of the    elements, or a combination thereof.-   E33. A process to activate a catalyst system, comprising combining    an activator with a catalyst compound according to any one of    Embodiments E1 to E20.-   E34. A process to activate a catalyst system comprising combining an    activator with a catalyst compound represented by the formula:

-   wherein each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination; wherein M is a Group 3, 4, 5 or 6    transition metal; wherein N¹ and N² are nitrogen and O¹ and O² are    oxygen; wherein each of X¹ and X² is, independently, a univalent C₁    to C₂₀ hydrocarbyl radical, a functional group comprising elements    from Groups 13-17 of the periodic table of the elements, or X¹ and    X² join together to form a C₄ to C₆₂ cyclic or polycyclic ring    structure; wherein Y comprises an sp³ carbon directly bonded to N²    and is selected from the group consisting of divalent C₁ to C₄₀    hydrocarbyl radicals, divalent functional groups comprising elements    from Groups 13-17 of the periodic table of the elements, and    combinations thereof; and wherein each of R¹, R², R³, R⁴, R⁵, R⁶,    R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R¹² may independently join together to form a C₄ to C₆₂ cyclic    or polycyclic ring structure.-   E35. The process according to Embodiment E33 or Embodiment E34    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-mer arrangement.-   E36. The process according to Embodiment E33 or Embodiment E34    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a mer-fac arrangement.-   E37. The process according to Embodiment E33 or Embodiment E34    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-fac arrangement.-   E38. The process according to any one of Embodiments E33 to E37    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer    arrangement.-   E39. The process according to any one of Embodiments E33 to E37    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a mer-fac    arrangement.-   E40. The process according to any one of Embodiments E33 to E37    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-fac    arrangement.-   E41. The process according to any one of Embodiments E33 to E40    wherein a salen ligand and a metalation reagent are contacted to    form the catalyst compound prior to combination with the activator    and subsequently with the activator without isolation of the    catalyst compound.-   E42. The process according to any one of Embodiments E33 to E40,    wherein a salen ligand and a metalation reagent are contacted to    form the catalyst compound in the presence of the activator, in the    presence of one or more olefins, or a combination thereof.-   E43. A process to polymerize olefins comprising contacting one or    more olefins with a catalyst system according to any one of    Embodiments E21 to E32 at polymerization conditions to produce a    polyolefin.-   E44. A process to polymerize olefins comprising: contacting one or    more olefins with a catalyst system at polymerization conditions to    produce a polyolefin, the catalyst system comprising an activator    and a catalyst compound represented by the formula:

-   wherein each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination; wherein M is a Group 3, 4, 5 or 6    transition metal; wherein N¹ and N² are nitrogen and O¹ and O² are    oxygen; wherein each of X¹ and X² is, independently, a univalent C₁    to C₂₀ hydrocarbyl radical, a functional group comprising elements    from Groups 13-17 of the periodic table of the elements, or X¹ and    X² join together to form a C₄ to C₆₂ cyclic or polycyclic ring    structure, provided however if M is trivalent X² is not present;    wherein Y comprises an sp³ carbon directly bonded to N² and is    selected from the group consisting of divalent C₁ to C₄₀ hydrocarbyl    radicals, divalent functional groups comprising elements from Groups    13-17 of the periodic table of the elements, and combinations    thereof; and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,    R¹⁰, R¹¹, and R¹² is, independently, a hydrogen, a C₁-C₄₀    hydrocarbyl radical, a functional group comprising elements from    Group 13-17 of the periodic table of the elements, or two or more of    R¹ to R¹² may independently join together to form a C₄ to C₆₂ cyclic    or polycyclic ring structure.-   E45. The process according to Embodiment E43 or Embodiment E44    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-mer arrangement.-   E46. The process according to Embodiment E43 or Embodiment E44    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a mer-fac arrangement.-   E47. The process according to Embodiment E43 or Embodiment E44    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-fac arrangement.-   E48. The process according to any one of Embodiments E43 to E47    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer    arrangement.-   E49. The process according to any one of Embodiments E43 to E47    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a mer-fac    arrangement.-   E50. The process according to any one of Embodiments E43 to E47    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²O²] into a fac-fac    arrangement.-   E51. A process to polymerize olefins comprising: contacting a salen    ligand with a metalation reagent to produce a catalyst precursor;    and contacting the catalyst precursor with an activator and one or    more olefins at polymerization conditions to produce a polyolefin;    wherein the salen ligand is represented by the formula:

-   -   wherein the metalation reagent is represented by the formula:        MX¹X²X³X⁴    -   wherein the catalyst precursor is represented by the formula:

-   wherein each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination; wherein n is 1 or 2; wherein M is a    Group 3, 4, 5 or 6 transition metal, provided however where n is 1    then X² is not present; wherein N¹ and N² are nitrogen and O¹ and O²    are oxygen; wherein each of X¹ and X² (where present) is,    independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a    functional group comprising elements from Groups 13-17 of the    periodic table of the elements, or X¹ and X² if present may join    together to form a C₄ to C₆₂ cyclic or polycyclic ring structure;    wherein Y comprises an sp³ carbon directly bonded to N² and is    selected from the group consisting of divalent C₁ to C₄₀ hydrocarbyl    radicals, divalent functional groups comprising elements from Groups    13-17 of the periodic table of the elements, and combinations    thereof; and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,    R¹⁰, R¹¹, and R¹² is independently, a hydrogen, a C₁-C₄₀ hydrocarbyl    radical, a functional group comprising elements from Group 13-17 of    the periodic table of the elements, or two or more of R¹ to R¹² may    independently join together to form a C₄ to C₆₂ cyclic or polycyclic    ring structure.-   E52. A process to polymerize olefins comprising: contacting a salen    ligand with a metalation reagent to produce a catalyst precursor;    and contacting the catalyst precursor with an activator and one or    more olefins at polymerization conditions to produce a polyolefin;    wherein the salen ligand is represented by the formula:

-   -   wherein the metalation reagent is represented by the formula:        MX¹X²X³X⁴    -   wherein the catalyst precursor is represented by the formula:

-   wherein each solid line in the formulae represents a covalent bond    and each dashed line represents a bond having varying degrees of    covalency and a varying degree of coordination; wherein each of R¹,    R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is independently,    a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group    comprising elements from Group 13-17 of the periodic table of the    elements, or two or more of R¹ to R¹² may independently join    together to form a C₄ to C₆₂ cyclic or polycyclic ring structure.-   E53. The process according to any one of Embodiments E44 to E52,    wherein the polymerization conditions comprise a temperature of from    about 0° C. to about 300° C., a pressure from about 0.35 MPa to    about 10 MPa, and a time from about 0.1 minutes to about 24 hours.-   E54. The process according to any one of Embodiments E44 to E53    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-mer arrangement.-   E55. The process according to any one of Embodiments E44 to E53    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a mer-fac arrangement.-   E56. The process according to any one of Embodiments E44 to E53    wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-fac arrangement.-   E57. The process according to any one of Embodiments E44 to E56    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer    arrangement.-   E58. The process according to any one of Embodiments E44 to E56    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a mer-fac    arrangement.-   E59. The process according to any one of Embodiments E44 to E56    wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-fac    arrangement.-   E60. The process according to any one of Embodiments E44 to E59,    wherein the salen ligand and the metalation reagent are contacted    prior to combination with the activator and subsequently with the    activator without isolation of the catalyst compound.-   E61. The process according to any one of Embodiments E44 to E60,    wherein the salen ligand and the metalation reagent are contacted in    the presence of the activator, in the presence of one or more    olefins, or a combination thereof-   E62. The process according to any one of Embodiments E44 to E61,    wherein the one or more olefins comprise propylene.-   E63. The process according to any one of Embodiments E44 to E62,    wherein the one or more olefins comprise at least 50 mole %    propylene.-   E64. The process according to any one of Embodiments E44 to E63,    wherein the polyolefin comprises at least 50 mole % propylene having    a concentration of meso isotactic pentads [mmmm] of greater than or    equal to about 90 wt %, based on the total weight of the polymer.-   E65. The process according to any one of Embodiments E44 to E64,    wherein the polyolefin comprises greater than 95 wt % isotactic    polypropylene and has a melting point greater than or equal to about    160° C.-   E66. Polypropylene produced according to the process of any one of    Embodiments E44 to E65.-   E67. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 145° C.-   E68. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 148° C.-   E69. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 150° C.-   E70. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 152° C.-   E71. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 154° C.-   E72. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 155° C.-   E73. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 156° C.-   E74. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 157° C.-   E75. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 158° C.-   E76. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 159° C.-   E77. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 160° C.-   E78. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 161° C.-   E79. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 162° C.-   E80. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 163° C.-   E81. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 164° C.-   E82. The polypropylene according to Embodiment E66 having a melting    point determined using differential scanning calorimetry greater    than or equal to about 165° C.-   E83. The polypropylene according to any one of Embodiments E66 to    E82 having a melting point determined using differential scanning    calorimetry less than or equal to about 175° C.-   E84. The polypropylene according to any one of Embodiments E66 to    E82 having a melting point determined using differential scanning    calorimetry less than or equal to about 170° C.-   E85. The polypropylene according to any one of Embodiments E66 to    E82 having a melting point determined using differential scanning    calorimetry less than or equal to about 167° C.-   E86. The polypropylene according to any one of Embodiments E66 to    E82 comprising greater than 95 wt % isotactic polypropylene.-   E87. The polypropylene according to any one of Embodiments E66 to    E82 comprising greater than 96 wt % isotactic polypropylene.-   E88. The polypropylene according to any one of Embodiments E66 to    E82 comprising greater than 97 wt % isotactic polypropylene.-   E89. The polypropylene according to any one of Embodiments E66 to    E82 comprising greater than 98 wt % isotactic polypropylene.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. 28 illustrative catalyst compounds eachaccording to one or more embodiments according to the inventiondescribed, were synthesized, wherein M is Ti, Zr or Hf, as shown inTable 1. Several catalysts were employed as polymerization catalyst. Allpolymerization reactions were carried out at room temperature (25° C.)using 10 micromoles of the catalyst and 500 eq. MAO as an activatorunder a purified nitrogen atmosphere using standard glovebox, highvacuum or Schlenk techniques, unless otherwise noted. All solvents usedwere anhydrous, de-oxygenated and purified according to knownprocedures. All starting materials were either purchased from Aldrichand purified prior to use or prepared according to procedures known tothose skilled in the art.

TABLE 1

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example 8

Example 9

Example 10

Example 11

Example 12

Example 13

Example 14

Example 15

Example 16

Example 17

Example 18

Example 19

Example 20

Example 21

Example 22

Example 23

Example 24

Example 25

Example 26

Example 27

Example 28

Example 1

Synthesis of the ligand precursor (Lig¹H₂): A solution of2-aminobenzylamine (0.45 gram, 3.69 mmol) in methanol (20 mL) was addedto a solution of 3,5-dichlorosalicylaldehyde (1.40 gram, 7.38 mmol) inmethanol (20 mL) and the reaction mixture was stirred at roomtemperature until an orange solid precipitated. The solid was collectedby filtration, washed with cold methanol and dried yielding the ligandprecursor quantitatively.

¹H NMR (CDCl₃, 400 MHz): δ=8.33 (s, 1H, NCH), 8.16 (s, 1H, NCH), 7.64(d, 1H, J=2.5 Hz, ArH), 7.57 (d, 1H, J=2.5 Hz, ArH), 7.53-6.91 (m, 6H,ArH), 4.85 (s, 2H, CH₂).

Synthesis of Lig¹ HfBn₂: Lig¹H₂ (87 mg, 0.18 mmol) was dissolved inabout 1 mL of toluene and added dropwise to a stirring yellow solutionof HfBn₄ (101 mg, 0.18 mmol) in about 1 mL of toluene. The color of thesolution changed to dark orange. The reaction mixture was stirred atroom temperature for 2 hours the solvent was removed under vacuum. Theremaining solid was washed with 1 mL of pentane and dried, yielding anorange solid quantitatively.

¹H NMR (C₆D₆, 400 MHz): δ=7.36 (s, 1H, NCH), δ=7.29 (s, 1H, NCH), 7.20(d, 1H, J=1.8 Hz, ArH), 7.19-6.89 (m, 18H, ArH), 6.53 (d, 1H, J=1.8 Hz,ArH), 6.37 (d, J=1.8 Hz, 1H), 5.13 (d, J=9.7 Hz, 1H, CH), 4.98 (d, J=9.7Hz, 1H, CH), 4.25 (d, J=12.0 Hz, 1H, CH), 3.62 (d, J=11.2 Hz, 1H, CH),3.19 (d, J=11.2 Hz, 1H, CH), 3.08 (d, J=12.0 Hz, 1H, CH).

Example 2

Synthesis of the ligand precursor (Lig²H₂): A solution of2-aminobenzylamine (0.49 gram, 4.00 mmol) in methanol (20 mL) was addedto a solution of 5-chlorosalicylaldehyde (1.27 gram, 8.00 mmol) inmethanol (20 mL) and the reaction mixture was stirred at roomtemperature until an orange solid precipitated. The solid was collectedby filtration, washed with cold methanol and dried yielding the ligandprecursor quantitatively.

¹H NMR (CDCl₃, 200 MHz): δ=8.37 (s, 1H, NCH), 8.24 (s, 1H, NCH),7.32-6.71 (m, 10H, ArH), 4.81 (s, 2H, CH₂).

Example 3

Synthesis of the ligand precursor (Lig³H₂): A solution of2-aminobenzylamine (0.29 gram, 2.38 mmol) in methanol (20 mL) was addedto a solution of 3,5-dibromosalicylaldehyde (1.33 gram, 4.76 mmol) inmethanol (20 mL) and the reaction mixture was stirred at roomtemperature until an orange solid precipitated. The solid was collectedby filtration, washed with cold methanol and dried yielding the ligandprecursor quantitatively.

¹H NMR (CDCl₃, 200 MHz): δ=8.30 (s, 1H, NCH), 8.24 (s, 1H, NCH), 7.59(d, 1H, J=2.5 Hz, ArH), 7.48 (d, 1H, J=2.5 Hz, ArH), 7.53-6.91 (m, 6H,ArH), 4.78 (s, 2H, CH₂).

Example 4

Synthesis of the ligand precursor (Lig⁴H₂): Lig⁴H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.28 gram, 2.29 mmol) and 3,5-diiodosalicylaldehyde(1.71 gram, 4.58 mmol).

Synthesis of Lig⁴Ti(OiPr)₂: Lig⁴H₂ (143 mg, 0.17 mmol) was dissolved in1 mL of toluene and added dropwise to a stirring solution of Ti(OiPr)₄(49 mg, 0.17 mmol) in 1 mL of toluene. The reaction mixture was stirredat room temperature and after 2 hours the solvent was removed undervacuum, and the solid was washed with 1 mL of pentane and dried,yielding a yellow solid quantitatively.

¹H NMR (C₆D₆, 400 MHz): δ=8.13 (d, 1H, J=2.2 Hz, ArH), 8.11 (d, 1H,J=2.2 Hz, ArH), 7.22 (s, 1H, NCH), 7.18 (d, 1H, J=2.2 Hz, ArH), 7.01 (s,1H, NCH), 7.98 (d, 1H, J=2.2 Hz, ArH), 6.96-6.72 (m, 4H, ArH), 4.76(sept, J=6.1 Hz, 1H, CH), 4.21 (d, J=14.0 Hz, 1H, CH), 3.78 (sept, J=6.1Hz, 1H, CH), 3.43 (d, J=14.0 Hz, 1H, CH), 1.19 (d, J=6.1 Hz, 3H, CH₃),1.03 (d, J=6.1 Hz, 3H, CH₃), 0.64 (d, J=6.1 Hz, 3H, CH₃), 0.45 (d, J=6.1Hz, 3H, CH₃).

Example 5

Synthesis of the ligand precursor (Lig⁵H₂): Lig⁵H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.32 gram, 2.61 mmol) and 3-methylsalicylaldehyde(0.71 gram, 5.22 mmol).

¹H NMR (CDCl₃, 200 MHz): δ=8.45 (s, 1H, NCH), 8.35 (s, 1H, NCH),7.33-6.60 (m, 10H, ArH), 4.84 (s, 2H, CH₂), 2.20 (s, 3H, CH₃), 2.13 (s,3H, CH₃).

Example 6

Synthesis of the ligand precursor (Lig⁶H₂): Lig⁶H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.30 gram, 2.43 mmol) and 5-methylsalicylaldehyde(0.66 gram, 4.86 mmol).

Example 7

Synthesis of the ligand precursor (Lig⁷H₂): A solution of2-aminobenzylamine (0.57 gram, 4.67 mmol) in methanol (20 mL) was addedto a solution of salicylaldehyde (1.15 gram, 9.34 mmol) in methanol (20mL) and the reaction mixture was stirred at room temperature for 2hours. The solvent was removed under vacuum yielding the ligandprecursor quantitatively as orange oil.

Example 8

Synthesis of the ligand precursor (Lig⁸H₂): Lig⁸H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.28 gram, 2.30 mmol) and3-methoxy-5-bromosalicylaldehyde (1.06 gram, 4.60 mmol).

¹H NMR (CDCl₃, 200 MHz): δ=8.35 (s, 1H, NCH), 8.21 (s, 1H, NCH),7.31-7.20 (m, 3H, ArH), 7.03-6.94 (m, 3H, ArH), 6.83-6.78 (m, 2H, ArH),4.84 (s, 2H, CH₂), 3.82 (s, 3H, OCH₃), 3.73 (s, 3H, OCH₃).

Example 9

Synthesis of the ligand precursor (Lig⁹H₂): Lig⁹H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.41 gram, 3.39 mmol) and3-isopropyl-5-chloro-6-methylsalicylaldehyde (1.44 gram, 6.78 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=14.7 (s, 1H, OH), 14.4 (s, 1H, OH), 8.92 (s,1H, NCH), 8.88 (s, 1H, NCH), 7.45-7.13 (m, 6H, ArH), 4.96 (s, 2H, CH₂),3.40 (sept, 1H, J=7.5 Hz, CH), 3.22 (sept, 1H, J=7.5 Hz, CH), 2.51 (s,3H, CH₃), 2.38 (s, 3H, CH₃), 1.25 (d, 6H, J=7.5 Hz, CH₃), 1.17 (d, 6H,J=7.5 Hz, CH₃).

Example 10

Synthesis of the ligand precursor (Lig¹⁹H₂): Lig¹⁰H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (2.44 gram, 0.02 mol) and3,5-di-tert-butylsalicylaldehyde (9.36 gram, 0.04 mol).

¹H NMR (CDCl₃, 400 MHz): δ=8.58 (s, 1H, NCH), 8.52 (s, 1H, NCH), 7.47(d, 1H, J=2.3 Hz, ArH), 7.45 (m, 1H, ArH), 7.36 (m, 1H, ArH), 7.33 (d,1H, J=2.3 Hz, ArH), 7.28 (m, 1H, ArH), 7.22 (d, 1H, J=2.3 Hz, ArH), 7.13(m, 1H, ArH), 7.00 (d, 1H, J=2.3 Hz, ArH), 4.93 (s, 2H, CH₂), 1.49 (s,9H, CH₃), 1.40 (s, 9H, CH₃), 1.32 (s, 9H, CH₃), 1.25 (s, 9H, CH₃).

Synthesis of Lig¹⁰ZrBn₂: Lig¹⁰H₂ (35 mg, 0.06 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of ZrBn₄ (29 mg,0.06 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

Synthesis of Lig¹⁰HfBn₂: Lig¹⁰H₂ (48 mg, 0.09 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of HfBn₄ (47 mg,0.09 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

¹H NMR (C₆D₆, 400 MHz): δ=8.11 (s, 1H, NCH), 7.78 (d, 1H, J=1.7 Hz,ArH), 7.70 (s, 1H, NCH), 7.65 (d, 1H, J=1.7 Hz, ArH), 7.09-6.43 (m, 16H,ArH), 4.23 (d, J=13.4 Hz, 1H, CH), 3.48 (d, J=13.4 Hz, 1H, CH), 2.77 (d,J=8.3 Hz, 1H, CH), 2.70 (d, J=8.3 Hz, 1H, CH), 1.79 (d, J=9.1 Hz, 1H,CH), 1.64 (s, 9H, CH₃), 1.58 (s, 9H, CH₃), 1.61 (s, 18H, CH₃), 0.62 (d,J=9.1 Hz, 1H, CH).

Synthesis of Lig¹⁰Ti(OiPr)₂: Lig¹⁰H₂ (51 mg, 0.09 mmol) was dissolved in1 mL of toluene and added dropwise to a stirring solution of Ti(OiPr)₄(26 mg, 0.09 mmol) in 1 mL of toluene. The reaction mixture was stirredat room temperature and after 2 hours the solvent was removed undervacuum, and the solid was washed with 1 mL of pentane and dried,yielding a yellow solid quantitatively.

¹H NMR (C₆D₆, 200 MHz): δ=7.81 (s, 1H, NCH), 7.76 (d, 1H, J=1.3 Hz,ArH), 7.71 (d, 1H, J=1.3 Hz, ArH), 7.69 (s, 1H, NCH), 7.10-7.04 (m, 4H,ArH), 6.95-6.88 (m, 2H, ArH), 4.92 (sept, J=6.0 Hz, 1H, CH), 4.59 (d,J=12.2 Hz, 1H, CH), 3.61 (sept, J=6.0 Hz, 1H, CH), 3.47 (d, J=12.2 Hz,1H, CH), 1.76 (s, 9H, CH₃), 1.68 (s, 9H, CH₃), 1.32 (s, 9H, CH₃), 1.29(s, 9H, CH₃), 1.11 (d, J=6.0 Hz, 3H, CH₃), 1.06 (d, J=6.0 Hz, 3H, CH₃),0.57 (d, J=6.0 Hz, 3H, CH₃), 0.43 (d, J=6.0 Hz, 3H, CH₃).

Synthesis of Lig¹⁰Zr(OtBu)₂: Lig¹⁰H₂ (49 mg, 0.09 mmol) was dissolved in1 mL of toluene and added dropwise to a stirring solution of Zr(OtBu)₄(34 mg, 0.09 mmol) in 1 mL of toluene. The reaction mixture was stirredat room temperature and after 2 hours the solvent was removed undervacuum, and the solid was washed with 1 mL of pentane and dried,yielding a yellow solid quantitatively.

¹H NMR (C₆D₆, 400 MHz): δ=7.86 (s, 1H, NCH), 7.80 (d, 1H, J=1.0 Hz,ArH), 7.73 (d, 1H, J=1.0 Hz, ArH), 7.72 (s, 1H, NCH), 7.12-7.07 (m, 4H,ArH), 6.94-6.89 (m, 2H, ArH), 4.21 (d, J=13.0 Hz, 1H, CH), 3.61 (d,J=13.0 Hz, 1H, CH), 1.78 (s, 9H, CH₃), 1.65 (s, 9H, CH₃), 1.30 (s, 9H,CH₃), 1.27 (s, 9H, CH₃), 1.20 (s, 9H, CH₃), 0.69 (s, 9H, CH₃).

Example 11

Synthesis of the ligand precursor (Lig¹¹H₂): Lig¹¹H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (1.00 gram, 8.19 mmol) and3-tert-butylsalicylaldehyde (2.92 gram, 16.38 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.58 (s, 1H, NCH), 8.51 (s, 1H, NCH),7.45-7.04 (m, 8H, ArH), 6.87 (t, 1H, J=7.6 Hz, ArH), 6.76 (t, 1H, J=7.6Hz, ArH), 4.95 (s, 2H, CH₂), 1.47 (s, 9H, CH₃), 1.39 (s, 9H, CH₃).

Synthesis of Lig¹¹ HfBn₂: Lig¹¹H₂ (68 mg, 0.15 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of HfBn₄ (84 mg,0.15 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

¹H NMR (C₆D₆, 400 MHz): δ=8.10 (s, 1H, NCH), 7.68 (s, 1H, NCH),7.48-7.43 (m, 5H, ArH), 7.05-6.44 (m, 15H, ArH), 4.10 (d, J=13.8 Hz, 1H,CH), 3.41 (d, J=13.8 Hz, 1H, CH), 2.81 (d, J=8.3 Hz, 1H, CH), 2.71 (d,J=8.3 Hz, 1H, CH), 2.03 (d, J=10.4 Hz, 1H, CH), 1.61 (s, 9H, CH₃), 1.53(s, 9H, CH₃), 1.06 (d, J=10.4 Hz, 1H, CH).

Example 12

Synthesis of the ligand precursor (Lig¹²H₂): Lig¹²H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.28 gram, 2.33 mmol) and3-tert-butyl-5-chlorosalicylaldehyde (0.99 gram, 4.66 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.48 (s, 1H, NCH), 8.41 (s, 1H, NCH),7.42-7.32 (m, 5H, ArH), 7.21 (d, 1H, J=2.4 Hz, ArH), 7.19 (d, 1H, J=2.4Hz, ArH), 7.01 (d, 1H, J=2.4 Hz, ArH), 4.94 (s, 2H, CH₂), 1.45 (s, 9H,CH₃), 1.35 (s, 9H, CH₃).

Synthesis of Lig¹²HfBn₂: Lig¹²H₂ (80 mg, 0.16 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of HfBn₄ (85 mg,0.16 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

¹H NMR (C₆D₆, 400 MHz): δ=7.74 (s, 1H, NCH), δ=7.55 (s, 1H, NCH), 7.51(d, 1H, J=1.9 Hz, ArH), 7.48 (d, 1H, J=1.9 Hz, ArH), 7.10-6.61 (m, 16H,ArH), 4.95 (d, J=10.3 Hz, 1H, CH), 3.47 (d, J=10.3 Hz, 1H, CH), 2.61 (d,J=8.5 Hz, 1H, CH), 2.55 (d, J=8.5 Hz, 1H, CH), 2.01 (d, J=9.3 Hz, 1H,CH), 1.39 (s, 9H, CH₃), 1.33 (s, 9H, CH₃), 0.92 (d, J=9.3 Hz, 1H, CH).

Example 13

Synthesis of the ligand precursor (Lig¹³H₂): Lig¹³H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.29 gram, 2.35 mmol) and3-tert-butyl-5-methoxysalicylaldehyde (0.98 gram, 4.71 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.53 (s, 1H, NCH), 8.48 (s, 1H, NCH),7.45-7.12 (m, 4H, ArH), 7.05 (d, 1H, J=2.5 Hz, ArH), 6.93 (d, 1H, J=2.5Hz, ArH), 6.70 (d, 1H, J=2.5 Hz, ArH), 6.49 (d, 1H, J=2.5 Hz, ArH), 4.95(s, 2H, CH₂), 3.78 (s, 3H, OCH₃), 3.70 (s, 3H, OCH₃), 1.46 (s, 9H, CH₃),1.37 (s, 9H, CH₃).

Synthesis of Lig¹³HfBn₂: Lig¹³H₂ (86 mg, 0.17 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of HfBn₄ (93 mg,0.17 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

Example 15

Synthesis of the ligand precursor (Lig¹⁵H₂): Lig¹⁵H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.31 gram, 2.57 mmol) and 3-phenylsalicylaldehyde(1.02 gram, 5.15 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.63 (s, 1H, NCH), 8.52 (s, 1H, NCH),7.67-7.14 (m, 14H, ArH), 7.02 (t, 1H, J=7.6 Hz, ArH), 6.90 (t, 1H, J=7.6Hz, ArH), 4.95 (s, 2H, CH₂).

Example 16

Synthesis of the ligand precursor (Lig¹⁶H₂): Lig¹⁶H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.09 gram, 0.75 mmol) and3-(1-adamantyl)-5-methylsalicylaldehyde (0.40 gram, 1.50 mmol).

¹H NMR (CDCl₃, 200 MHz): δ=8.47 (s, 1H, NCH), 8.33 (s, 1H, NCH),7.39-6.70 (m, 8H, ArH), 4.67 (s, 2H, CH₂), 2.27 (s, 3H, CH₃), 2.20 (s,3H, CH₃), 2.12-1.95 (m, 18H, adamantyl), 1.75 (bs, 12H, adamantyl).

Synthesis of Lig¹⁶HfBn₂: Lig¹⁶H₂ (51 mg, 0.08 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of HfBn₄ (44 mg,0.08 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

Example 17

Synthesis of the ligand precursor (Lig¹⁷H₂): Lig¹⁷H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.10 gram, 0.81 mmol) and3-(2-adamantyl)-5-methylsalicylaldehyde (0.44 gram, 1.62 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.47 (s, 1H, NCH), 8.41 (s, 1H, NCH),7.49-7.35 (m, 4H, ArH), 7.09 (d, 1H, J=1.9 Hz, ArH), 7.08 (d, 1H, J=1.9Hz, ArH), 7.00 (d, 1H, J=2.1 Hz, ArH), 6.78 (d, 1H, J=2.1 Hz, ArH), 4.90(s, 2H, CH₂), 2.32 (s, 3H, CH₃), 2.26 (s, 3H, CH₃), 2.05-1.63 (m, 30H,2-adamantyl).

Example 18

Synthesis of the ligand precursor (Lig¹⁸H₂): Lig¹⁸H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.89 gram, 7.32 mmol) and3-(1-adamantyl)-5-chlorosalicylaldehyde (4.25 gram, 14.64 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.46 (s, 1H, NCH), 8.40 (s, 1H, NCH),7.39-7.27 (m, 5H, ArH), 7.17 (d, 1H, J=2.0 Hz, ArH), 7.14 (d, 1H, J=2.0Hz, ArH), 6.97 (d, 1H, J=2.0 Hz, ArH), 4.93 (s, 2H, CH₂), 2.17-2.03 (m,18H, adamantyl), 1.79-1.73 (m, 12H, adamantyl).

Example 19

Synthesis of the ligand precursor (Lig¹⁹H₂): Lig¹⁹H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.17 gram, 1.38 mmol) and3-(1-adamantyl)-5-methoxysalicylaldehyde (0.79 gram, 2.76 mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.51 (s, 1H, NCH), 8.45 (s, 1H, NCH),7.44-7.12 (m, 4H, ArH), 6.99 (d, 1H, J=2.1 Hz, ArH), 6.86 (d, 1H, J=2.1Hz, ArH), 6.69 (d, 1H, J=2.1 Hz, ArH), 6.45 (d, 1H, J=2.1 Hz, ArH), 4.95(s, 2H, CH₂), 3.77 (s, 3H, OCH₃), 3.69 (s, 3H, OCH₃), 2.20-2.03 (m, 18H,adamantyl), 1.79-1.74 (m, 12H, adamantyl).

Synthesis of Lig¹⁹HfBn₂: Lig¹⁹H₂ (67 mg, 0.10 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring red solution of HfBn₄ (55mg, 0.10 mmol) in 1 mL of toluene. The color of the solution changed todark orange. The reaction mixture was stirred at room temperature andafter 2 hours the solvent was removed under vacuum, and the solid waswashed with 1 mL of pentane and dried, yielding an orange solidquantitatively.

Example 20

Synthesis of the ligand precursor (Lig²⁰H₂): Lig²⁰H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.22 gram, 1.83 mmol) and3-(2-adamantyl)-5-chlorosalicylaldehyde (1.06 gram, 3.66 mmol).

Example 21

Synthesis of the ligand precursor Lig²¹H₂): Lig²¹H₂ was prepared inquantitative yield according to the procedure of Example 1, using2-aminobenzylamine (0.10 gram, 0.79 mmol) and 3,5-dicumylsalicylaldehyde(0.57 gram, 0.20 mmol).

Example 22

Synthesis of the ligand precursor (Lig²²H₂): A solution of3,5-dichlorosalicylaldehyde (0.21 gram, 1.01 mmol) in cold methanol (20mL) was added very slowly to a solution of 2-aminobenzylamine (0.13gram, 1.01 mmol) in methanol (20 mL) at 0° C. and the reaction mixturewas stirred for 5 hours until a bright yellow solid appeared. The solidwas collected by filtration, washed with cold methanol and dried. Asolution of this mono-substituted intermediate material (0.06 gram, 0.27mmol) in methanol (20 mL) was added to a solution of3,5-di-tert-butylsalicylaldehyde (0.08 gram, 0.27 mmol) in methanol (20mL) and the reaction mixture was stirred at room temperature for 24hours. The orange solid was collected by filtration, washed with coldmethanol and dried yielding the ligand precursor quantitatively.

¹H NMR (CDCl₃, 400 MHz): δ=8.53 (s, 1H, NCH), 8.40 (s, 1H, NCH), 7.49(d, 1H, J=1.9 Hz, ArH), 7.42-7.39 (m, 4H, ArH), 7.33 (d, 1H, J=1.9 Hz,ArH), 7.18 (d, 1H, J=1.9 Hz, ArH), 7.02 (d, 1H, J=1.9 Hz, ArH), 4.96 (s,2H, CH₂), 1.50 (s, 9H, CH₃), 1.32 (s, 9H, CH₃).

Example 23-28

Prepared According Procedure of Example22.

Lig²³H₂: ¹H NMR (CDCl₃, 400 MHz): δ=8.51 (s, 1H, NCH), 8.37 (s, 1H,NCH), 7.61 (d, 1H, J=1.9 Hz, ArH), 7.49 (d, 1H, J=1.9 Hz, ArH),7.44-7.39 (m, 3H, ArH), 7.18-7.10 (m, 3H, ArH), 4.97 (s, 2H, CH₂), 1.49(s, 9H, CH₃), 1.30 (s, 9H, CH₃).

Lig²⁵H₂: Lig²⁵H₂ was prepared in quantitative yield according to theprocedure of Example 22, using2-(((aminomethyl)phenylimino)methyl)-4,6-dichlorophenol (0.38 gram, 1.28mmol) and 3-(2-adamantyl)-5-methylsalicylaldehyde (0.35 gram, 1.28mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.49 (s, 1H, NCH), 8.40 (s, 1H, NCH), 7.46(d, 1H, J=2.3 Hz, ArH), 7.36 (d, 1H, J=2.3 Hz, ArH), 7.35-7.10 (m, 4H,ArH), 7.03 (d, 1H, J=1.8 Hz, ArH), 6.82 (d, 1H, J=1.8 Hz, ArH), 4.91 (s,2H, CH₂), 2.24 (s, 3H, CH₃), 2.09 (bs, 6H, adamantyl), 2.04 (bs, 3H,adamantyl), 1.75 (bs, 6H, adamantyl).

Synthesis of Lig²⁵HfBn₂: Lig²⁵H₂ (52 mg, 0.10 mmol) was dissolved in 1mL of toluene and added dropwise to a stirring solution of HfBn₄ (52 mg,0.10 mmol) in 1 mL of toluene. The color of the solution changed to darkorange. The reaction mixture was stirred at room temperature and after 2hours the solvent was removed under vacuum, and the solid was washedwith 1 mL of pentane and dried, yielding an orange solid quantitatively.

Lig²⁶H₂: Lig²⁶H₂ was prepared in quantitative yield according to theprocedure of Example 22, using2-(((aminomethyl)phenylimino)methyl)-4,6-dibromophenol (0.32 gram, 0.83mmol) and 3-(2-adamantyl)-5-methylsalicylaldehyde (0.22 gram, 0.83mmol).

¹H NMR (CDCl₃, 400 MHz): δ=8.44 (s, 1H, NCH), 8.40 (s, 1H, NCH), 7.74(d, 1H, J=2.3 Hz, ArH), 7.44 (d, 1H, J=2.3 Hz, ArH), 7.35 (m, 2H, ArH),7.15 (m, 2H, ArH), 7.03 (d, 1H, J=1.8 Hz, ArH), 6.75 (d, 1H, J=1.8 Hz,ArH), 4.90 (s, 2H, CH₂), 2.24 (s, 3H, CH₃), 2.09 (bs, 6H, adamantyl),2.04 (bs, 3H, adamantyl), 1.75 (bs, 6H, adamantyl).

Molecular structure as determined by single crystal X-ray diffraction inORTEP format of five of the imino-phenylene-alkylene-imino salen ligandcatalysts, in which alkylene moiety Y is methylene, are shown in FIGS.1, 2, 3, 4, 5, and 6.

FIG. 1 shows the X-ray crystal structure of the imino-benzylimino salencatalyst according to Example 4, where the metal is Ti and where thebenzyl groups are replaced by O-iPr according to the following formula:

The structure in FIG. 1 is shown with the isopropyl group of each of theisopropoxy groups omitted for clarity.

FIG. 2 shows the X-ray crystal structure of the imino-benzylimino salencatalyst according to Example 10, where the metal is Zr and where thebenzyl groups are replaced by O-tBu according to the following formula:

The structure in FIG. 2 is shown with the tertiary butyl group of eachof the tertiary butoxy groups omitted for clarity.

FIG. 3 shows the X-ray crystal structure of the imino-benzylimino salencatalyst according to Example 10, where the metal is Ti and where thebenzyl groups are replaced by O-iPr according to the following formula:

The structure in FIG. 3 is shown with the isopropyl group of each of theisopropoxy groups omitted for clarity.

FIG. 4 shows the X-ray crystal structure of the imino-benzylimino salencatalyst according to Example 10, where the metal is Hf, according tothe following formula:

FIG. 5 shows the X-ray crystal structure of the imino-benzylimino salencatalyst shown in FIG. 4 with the phenyl rings of each of the benzylgroups omitted for clarity.

FIG. 6 shows the X-ray crystal structure of the imino-benzylimino salencatalyst according to Example 25, where the metal is Ti and where thebenzyl groups are replaced by O-iPr, according to the following formula:

The structure in FIG. 6 is shown with the isopropyl group of each of theisopropoxy groups omitted for clarity. As the FIGs. show, theimino-phenylene-alkylene-imino salen ligands according to someembodiments according to the invention produce catalysts having afac-mer wrapping conformation.

Examples 29 and 30

Synthesis of polypropylene using Lig¹⁰HfBn₂: MAO from Albemarle (30% byweight in toluene) was dried under vacuum at elevated temperature(generally 60 to 80° C.) overnight. The solid product was collected andused in the following reactions without further alteration.

Example 29

Solid MAO (359 mg), Lig¹⁰HfBn₂ (10 mg, 0.011 mmol), and a stir bar wereadded to a PARR bomb chilled to −85° C. Condensed propylene (25.5 g, 606mmol) was poured into the PARR bomb. The bomb was sealed and set to stirat room temperature overnight. The bomb was vented and polymer (1.24 g)was collected. DSC: 1^(st) melt: 157° C.; 2^(nd) melt: 155° C.

Example 30

Solid MAO (341 mg), Lig¹⁰HfBn₂ (11 mg, 0.012 mmol), and a stir bar wereadded to a PARR bomb chilled to −85° C. Condensed propylene (25.5 g, 606mmol) was poured into the bomb. The bomb was sealed, placed in an oilbath and heated to 70° C. The reaction was left to stir for 1 hour. Thebomb was vented and polymer (0.54 g) was collected. DSC: 1^(st) melt:151° C.; 2^(11d) melt: 152° C.

Additional Syntheses of Polypropylene A series of polymerizationreactions were conducted using neat propylene and 500 eq. MAO at roomtemperature (25° C.) for 13 hours. These data are shown in Table 2.

TABLE 2 Catalyst C₃₌ Polymer T_(melt) ΔH [mmmm] Example M used (g)obtained (g) (° C.) (J/g)) (wt %) 1 Hf 8.12 0.52 153.5 94.0 90.5 1 Ti8.13 0.651 132.4 14.7 — (very broad) 2 Hf 6.78 0.188 148.7 11.6 — 3 Hf7.07 0.83 151.2 53.5 81.4 4 Hf 9.47 0.67 153.1 52.9 85.3− 4 Zr 9.720.536 137/149 5.9 — 5 Hf 9.39 0.108 143.8 29.8 63.9 6 Hf 9.96 0.135147.4 10.0 — 8 Hf 8.46 None — — — 10 Hf 9.37 0.28 165.8 94.3 98.77 10 Zr7.04 0.122 160.1 15.9 — 10 Ti 9.47 0.22 NC — — 13 Hf 7.28 0.22 155.610.9 — 16 Hf 8.21 0.116 161.6 86.7 98.73 19 Hf 7.96 1.58 159.7 95.4 99.419 Zr 7.15 0.30 — — — 21 Hf 2.32 0.1 NC NC ~83 25 Hf 8.37 3.23 149.8 —96.35 26 Hf 11.7 1.14 153.18 73.36 97.75 27 Hf 6.95 0.29 157.04 77.3895.60

As these data show, the catalyst compounds, catalyst systems, andpolymerization processes disclosed herein provide novel and improvedcatalyst and systems for the polymerization of olefins, which producepolymers having improved properties, such as high polymer melting pointand highly isotactic polymers.

The crystallographic techniques indicate that the appended ring systemor systems are oriented fac-mer. The catalysts according to the instantdisclosure are believed to have a structure which provides a broadcorridor for the polymeryl moiety to reside and for the monomer toinsert during the polymerization process. As such, catalysts accordingto embodiments of the instant disclosure provide for an ability tocontrol one or more characteristics of polymerization, tacticity,comonomer insertion, and the like. All documents described herein areincorporated by reference herein, including any priority documentsand/or testing procedures to the extent they are not inconsistent withthis text, provided however that any priority document not named in theinitially filed application or filing documents is NOT incorporated byreference herein. As is apparent from the foregoing general descriptionand the specific embodiments, while forms according to the inventionhave been illustrated and described, various modifications can be madewithout departing from the spirit and scope according to the invention.Accordingly, it is not intended that the invention be limited thereby.

What is claimed is:
 1. A catalyst compound represented by the formula:

comprising [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-facarrangement or a fac-fac arrangement; wherein each solid line representsa covalent bond and each dashed line represents a bond having varyingdegrees of covalency and a varying degree of coordination; wherein M isa Group 4, 5 or 6 transition metal; wherein N¹ and N² are nitrogen andO¹ and O² are oxygen; wherein each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; wherein Y comprises an sp³ carbon directly bonded to N² andis selected from the group consisting of divalent C₁ to C₄₀ hydrocarbylradicals, divalent functional groups comprising elements from Groups13-17 of the periodic table of the elements, and combinations thereof;wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² is,independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functionalgroup comprising elements from Group 13-17 of the periodic table of theelements, or two or more of R¹ to R¹² may independently join together toform a C₄ to C₆₂ cyclic or polycyclic ring structure.
 2. The catalystcompound of claim 1, wherein [O¹,N¹,N²]—[N¹,N²,O²] are in a fac-merarrangement.
 3. The catalyst compound of claim 1, wherein M is Ti, Hf orZr.
 4. The catalyst compound of claim 1, wherein X¹ and X² are each abenzyl radical.
 5. The catalyst compound of claim 1, wherein each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is, independently,hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbyl radical.
 6. The catalystcompound of claim 1, wherein the sp³ carbon directly bonded to N² is abenzylic carbon.
 7. The catalyst compound of claim 1, wherein Y is adivalent aliphatic radical having from 1 to 10 carbon atoms.
 8. Thecatalyst compound of claim 1, wherein R¹¹ and R¹² join to form aphenylene ring directly bonded to N² and Y to form animino-phenylene-alkylene-imino bridged salen compound, represented bythe formula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵,and R¹⁶ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R¹⁰ and R¹³ to R¹⁶ mayindependently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure.
 9. The catalyst compound of claim 8, represented by theformula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, and R¹⁸ is independently, a hydrogen, a C₁-C₄₀ hydrocarbylradical, a functional group comprising elements from Group 13-17 of theperiodic table of the elements, or two or more of R¹ to R¹⁰ and R¹³ toR¹⁸ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.
 10. The catalyst compound of claim 9,wherein: X¹ and X² are benzyl radicals; at least one of R¹, R², R⁴, R⁵,R⁷, and R⁸ are independently selected from the group consisting of:C₁-C₁₀ alkyl, C₁-C₁₀ cycloalkyl, C₁-C₁₀ alkenyl C₁-C₁₀ alkoxy, arylsubstituted C₁-C₁₀ alkyl, C₁-C₁₀ aryl, halo, and combinations thereof;and R³, R⁶, R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are hydrogen. 11.The catalyst compound of claim 10, wherein at least one of R¹, R², R⁴,R⁵, R⁷, and R⁸ are independently selected from the group consisting of:methyl, ethyl, isopropyl, isobutyl, tertiary-butyl, isopentyl,2-methyl-2-phenylethyl; methoxy, benzyl, adamantyl, chloro, bromo, iodo,and combinations thereof.
 12. The catalyst compound of claim 9, whereinR² and R⁴ are identical, R⁵ and R⁷ are identical, or a combinationthereof.
 13. The catalyst compound of claim 8, wherein R¹⁴ and R¹⁵ jointo form a 2,3-naphthalenylene ring directly bonded to N² and Y to forman imino-naphthalenylene-alkylene-imino bridged salen compound,represented by the formula:

wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, R¹⁶, R¹⁹,R²⁰, R²¹, and R²² is, independently, a hydrogen, a C₁-C₄₀ hydrocarbylradical, a functional group comprising elements from Group 13-17 of theperiodic table of the elements, or two or more of R¹ to R¹⁰ and R¹³ toR¹⁶ may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.
 14. A catalyst system comprising: anactivator and a catalyst compound represented by the formula:

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen and comprising[O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement, or a mer-fac arrangementor a fac-fac arrangement, or wherein activation of the catalyst compoundrearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement, or amer-fac arrangement or a fac-fac arrangement; wherein each solid linerepresents a covalent bond and each dashed line represents a bond havingvarying degrees of covalency and a varying degree of coordination;wherein M is a Group 4, 5 or 6 transition metal; wherein each of X¹ andX² is, independently, a univalent C₁ to C₂₀ hydrocarbyl radical, afunctional group comprising elements from Groups 13-17 of the periodictable of the elements, or X¹ and X² join together to form a C₄ to C₆₂cyclic or polycyclic ring structure; wherein Y comprises an sp³ carbondirectly bonded to N² and is selected from the group consisting ofdivalent C₁ to C₄₀ hydrocarbyl radicals, divalent functional groupscomprising elements from Groups 13-17 of the periodic table of theelements, and combinations thereof; wherein each of R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² is, independently, a hydrogen, aC₁-C₄₀ hydrocarbyl radical, a functional group comprising elements fromGroup 13-17 of the periodic table of the elements, or two or more of R¹to R¹² may independently join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure.
 15. The catalyst system of claim 14,comprising [O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-facarrangement, or wherein activation of the catalyst compound rearranges[O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement or a mer-facarrangement.
 16. The catalyst system of claim 14, wherein the activatorcomprises alumoxane, a non-coordinating anion activator, or acombination thereof.
 17. The catalyst system of claim 14, wherein theactivator comprises alumoxane and the alumoxane is present at a ratio of1 mole aluminum or more per mole of catalyst compound.
 18. The catalystsystem of claim 14, wherein the activator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein Z is (L-H), or a reducible Lewis Acid, whereinL is a neutral Lewis base, H is hydrogen and (L-H)⁺is a Bronsted acid;wherein A^(d−)is a non-coordinating anion having the charge d⁻; and d isan integer from 1 to
 3. 19. The catalyst system of claim 14, wherein theactivator is represented by the formula:(Z)_(d) ⁺(A^(d−)) wherein A^(d−)is a non-coordinating anion having thecharge d⁻; wherein d is an integer from 1 to 3, and wherein Z is areducible Lewis acid represented by the formula: (Ar₃C⁺), where Ar isaryl radical, an aryl radical substituted with a heteroatom, an arylradical substituted with one or more C₁ to C₄₀ hydrocarbyl radicals, anaryl radical substituted with one or more functional groups comprisingelements from Groups 13-17 of the periodic table of the elements, or acombination thereof.
 20. A process to activate a catalyst system,comprising combining an activator with a catalyst compound representedby the formula:

wherein N¹ and N² are nitrogen and O¹ and O² are oxygen and comprising[O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-fac arrangementor a fac-fac arrangement, or wherein activation rearranges[O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement or a mer-facarrangement or a fac-fac arrangement; wherein M is a Group 4, 5 or 6transition metal; wherein each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; wherein Y comprises an sp³ carbon directly bonded to N² andis selected from the group consisting of divalent C₁ to C₄₀ hydrocarbylradicals, divalent functional groups comprising elements from Groups13-17 of the periodic table of the elements, and combinations thereof;and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, andR¹² is, independently, a hydrogen, a C₁-C₄₀ to hydrocarbyl radical, afunctional group comprising elements from Group 13-17 of the periodictable of the elements, or two or more of R¹ to R¹² may independentlyjoin together to form a C₄ to C₆₂ cyclic or polycyclic ring structure.21. The process of claim 20, comprising [O¹,N¹,N²]—[N¹,N²,O²] in afac-mer arrangement or a mer-fac arrangement, or wherein activationrearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-mer arrangement or a mer-facarrangement.
 22. A process to polymerize olefins comprising: contactingone or more olefins with a catalyst system at polymerization conditionsto produce a polyolefin, the catalyst system comprising an activator anda catalyst compound represented by the formula:

wherein M is a Group 4, 5 or 6 transition metal; wherein N¹ and N² arenitrogen and O¹ and O² are oxygen; wherein each of X¹ and X² is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or X¹ and X² join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; wherein Y comprises an sp³ carbon directlybonded to N² and is selected from the group consisting of divalent C₁ toC₄₀ hydrocarbyl radicals, divalent functional groups comprising elementsfrom Groups 13-17 of the periodic table of the elements, andcombinations thereof; and wherein each of R¹, R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, and R¹² is, independently, a hydrogen, a C₁-C₄₀ tohydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or two or more of R¹ to R¹²may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure.
 23. The process of claim 22, comprising[O¹,N¹,N²]—[N¹,N²,O²] in a fac-mer arrangement or a mer-fac arrangement;or wherein activation rearranges [O¹,N¹,N²]—[N¹,N²,O²] into a fac-merarrangement or a mer-fac arrangement.
 24. The process of claim 22,wherein the polymerization conditions comprise a temperature of fromabout 0° C. to about 300° C., a pressure from about 0.35 MPa to about 10MPa, and a time from about 0.1 minutes to about 24 hours.
 25. Theprocess of claim 22, wherein the polyolefin comprises at least 50 mole %propylene having a concentration of meso isotactic pentads [mmmm] ofgreater than or equal to about 90 wt %, based on the total weight of thepolymer.
 26. The process of claim 22 wherein the polyolefin comprisesisotactic polypropylene having a melting point greater than 160° C.